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.Keywords: electrostatic interaction; nanoparticles; non-close-packed monolayer; QCM-D; self-assembly; silica

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.

Iron oxide nanoparticles (FeOx-NP) are applied in medicine as contrast agents in magnetic resonance imaging (MRI) where they reduce the spin–spin relaxation time (T2-time) of absorbing tissue. Hence, control of their magnetic properties is essential for these applications. Magnetic properties strongly depend on the particle size and shape as well as the surface functionalization of the iron oxide nanoparticles. Especially, structural and magnetic disorder in the region close to the surface (1–2 nm) lead usually to a reduced magnetization compared to the corresponding bulk material. Therefore, X-ray magnetic circular dichroism (XMCD) in the total electron yield (TEY) mode is used to investigate local magnetic and electronic properties of the surface region of monodisperse, spherical FeOx-NPs (Fe3O4/γ-Fe2O3) before and after the postsynthetic treatment in oxygen-rich environment. Charge transfer multiplet calculations of the XMCD spectra are performed to analyze the contributions of Fe2+ and Fe3+ at different lattice sites, i.e., either in octahedral or tetrahedral environment. The analysis of the XMCD data reveals that both, the magnetization of the nanoparticle surface region as well as their maghemite to magnetite ratio, are strongly increased after tempering in an oxidative environment, which likely causes rearrangement of their crystalline order. The magnitude and the kinetics of these variables depend strongly on the particle size. In addition, after thermal annealing a reduced spin canting is extrapolated from the lower magnetic coercivity, which confirms that a structural rearrangement takes place.

Monodisperse small iron oxide nanoparticles functionalized with dendritic polyglycerol (dPG) or dendritic polyglycerol sulfate (dPGS) are prepared. They are highly stable in aqueous solutions as well as physiological media. In particular, oleic acid capped iron oxide particles (core diameter = 11 ± 1 nm) were modified by a ligand exchange process in a one pot synthesis with dPG and dPGS bearing phosphonate as anchor groups. Dynamic light scattering measurements performed in water and different biological media demonstrate that the hydrodynamic diameter of the particles is only slightly increased by the ligand exchange process resulting in a final diameter of less than 30 nm and that the particles are stable in these media. It is also revealed by magnetic resonance studies that their magnetic relaxivity is reduced by the surface modification but it is still sufficient for high contrast magnetic resonance imaging (MRI). Additionally, incubation of dPGS functionalized iron oxide nanoparticles with human umbilical vein endothelial cells showed a 50% survival at 85 nM (concentration of nanoparticles). Surface plasmon resonance (SPR) studies demonstrate that the dPGS functionalized iron oxide nanoparticles inhibit L-selectin ligand binding whereas the particles containing only dPG do not show this effect. Experiments in a flow chamber with human myelogenous leukemia cells confirmed L-selectin inhibition of the dPGS functionalized iron oxide nanoparticles and with that the L-selectin mediated leukocyte adhesion. These results indicate that dPGS functionalized iron oxide nanoparticles are a promising contrast agent for inflamed tissue probed by MRI.

Unprotected (“naked”) gold nanoparticles with high monodispersity (⟨d⟩, 5.5± 0.5 nm) were obtained in a facile and single-step microwave-assisted hydrolytic decomposition of the molecular precursor [NMe4][Au(CF3)2]. Given their chloride-free surface chemistry, the as-obtained gold nanoparticles were in situ functionalized with mono-, di-, and trivalent thiolated PEG ligands in order to study the influence of multivalent character of the ligands on the stability of the colloidal solutions. For this purpose, a novel tridentate ligand was synthesized and the previously reported syntheses of mono- and divalent thiol ligands were improved. Owing to the pristine character of the Au nanoparticles no ligand exchange was required, and the colloidal and chemical stability of the mono- and multivalent functionalized particles purely depended on the ligating ability of the thiolated groups. In situ-functionalized Au nanoparticles showed a strikingly (2 orders of magnitude higher) improved stability against small nucleophiles such as sodium cyanide compared to gold nanoparticles coated with citrate ligands and functionalized via a ligand-exchange reaction. The monovalent thiol PEG ligand produced most stable colloids against cyanide, which is explained by a strongly increased numerical ligand-density on the surface. Gold colloids stabilized by di- and trivalent ligands exhibited high stability in aqueous solutions with high NaCl concentrations (2 M) in contrast to those functionalized with the monovalent PEG ligand, which were only temporally stable in dilute NaCl solutions. The beneficial effect of the multivalence of the ligands was further demonstrated by the incorporation of an additional chelating ligand (dithiothreitol) to the colloidal dispersions.

In this study, the skin penetration and cellular uptake of amorphous silica particles with positive and negative surface charge and sizes ranging from 291 ± 9 to 42 ± 3 nm were investigated. Dynamic light scattering measurements and statistical analyses of transmission electron microscopy images were used to estimate the degree of particle aggregation, which was a key aspect to understanding the results of the in vitro cellular uptake experiments. Despite partial particle aggregation occurring after transfer in physiological media, particles were taken up by skin cells in a size-dependent manner. Functionalization of the particle surface with positively charged groups enhanced the in vitro cellular uptake. However, this positive effect was contrasted by the tendency of particles to form aggregates, leading to lower internalization ratios especially by primary skin cells. After topical application of nanoparticles on human skin explants with partially disrupted stratum corneum, only the 42 ± 3 nm particles were found to be associated with epidermal cells and especially dendritic cells, independent of their surface functionalization. Considering the wide use of nanomaterials in industries and the increasing interest for applications in pharmaceutics and cosmetics versus the large number of individuals with local or spread impairment of the skin barrier, e.g., patients with atopic dermatitis and chronic eczema, a careful dissection of nanoparticle-skin surface interactions is of high relevance to assess possible risks and potentials of intended and unintended particle exposure.Keywords: amorphous silica nanoparticles; colloidal stability; dendritic cells; HaCaT cells; keratinocytes; skin penetration

Approaches for the controlled formation of gold nanoparticle dimers are investigated. These are based on a locally confined surface modification of gold nanoparticles followed by bridging two particles with an organic linker. A key factor in these approaches is the use of multivalent ligands. Citrate-stabilized gold nanoparticles are immobilized on a glass surface and mono- and multivalent thiol ligands are investigated regarding their ability to inactivate the nanoparticles sites facing away from the glass. A successful locally confined functionalization is only possible if multivalent ligands are used in this step. The application of monovalent ligands results in less stable particles without a permanent regioselective functionalization. This result can be explained by the dynamic equilibrium between bound and free ligands. Subsequently, the sites of the nanoparticles previously bound to the glass surface are functionalized with thiol ligands additionally bearing a reactive group. Approaches using dithiol linkers, diamine linkers, and coupling complementary functionalized particles are investigated. The highest yield of stable dimers is obtained from conditions where nanoparticles which are regioselectively functionalized with an N-hydroxysuccinimide ester are reacted with complementary amino-functionalized particles. The application of nanoparticles with activated carboxyl groups is essential since standard carboxyl activation agents induce an aggregation of the nanoparticles due to a reaction with remaining citrate molecules on the nanoparticle surface which reduces significantly electrostatic stabilization. This versatile approach using complementary regioselective with multivalent ligands functionalized nanoparticles may be also used for the coupling of particles with different size, shape, or composition, as well as a control of the interparticle distance.