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The present work faces the rising demand of cationic particles of different sizes for biological applications, especially in gene therapies and nanotoxicology studies. A simple phase-transfer methodology has been developed for the functionalization of gold nanoparticles (Au NPs) with a variety of ligands, both cationic and anionic in aqueous solution, employing different nanocrystal sizes with narrow size distributions. Successful functionalization has been demonstrated by UV-vis spectroscopy, DLS, ζ-potential, and FTIR spectroscopy characterization of the particles before and after the phase transfer. The intracellular uptake of the differently charged Au NPs functionalized with peptidic biomolecules was investigated with human fibroblasts (1BR3G) by ICP-MS analysis of the digested cells and confocal fluorescence microscopy, which showed increased internalization of the cationic bioconjugates. Nuclear targeting could be observed by TEM, suggesting that the cationic peptidic biomolecule is acting as a nuclear localization signal.

The catalytic performance of ceria nanoparticles is generally attributed to active sites on the particle surface. The creation of oxygen vacancies and thus nonstoichiometric CeO2-¿ has been proposed to result in Ce3+ sites with unpaired f electrons which can be oxidized to spinless Ce4+ ions during catalytic reactions. We monitored the Ce electronic structure during the synthesis and catalase mimetic reaction of colloidal ceria nanoparticles under in situ conditions. By means of high-energy resolution hard X-ray spectroscopy, we directly probed the Ce 4f and 5d orbitals. We observe pronounced changes of the Ce 5d bands upon reduction of the particle size and during the catalytic reaction. The Ce 4f orbitals, however, remain unchanged, and we do not observe any significant number of spin-unpaired Ce3+ sites even for catalytically active small (3 nm) particles with large surface to bulk ratio. This confirms strong orbital mixing between Ce and O, and the Ce spin state is conserved during the reaction. The particles show an increase of the interatomic distances between Ce and O during the catalytic decomposition of hydrogen peroxide. The redox partner is therefore not a local Ce3+ site, but the electron density that is received and released during the catalytic reaction is delocalized over the atoms of the nanoparticle. This invokes the picture of an electron sponge. © 2013 American Chemical Society.

Colloidal gold nanoparticles (Au NPs) have been employed as single entities for rapid scanning and sequestration of Hg(II) from multicomponent aqueous solutions containing low pollutant concentrations. Under the studied conditions, sodium citrate has been identified as the reducing agent and Au NPs as the catalyst in the reduction of Hg(II), which is efficiently trapped in the presence of other cations such as Cu(II) and Fe(III). The effect of Hg(II) uptake implies amalgam formation, which leads to remarkable morphological transformations. The hydrophobicity of the resulting amalgam and consequent expulsion from water eases its recovery. The interaction between Au and Hg has been studied using UV-vis, ICP-MS, (S)TEM, SEM, EDX, and XRD.

Nanotoxicology is still a new discipline. In this Perspective, both its origins and its future trends are discussed. In particular, we note several issues we consider important for publications in this field.

In this work, we explore the formation of the protein corona after exposure of metallic Au nanoparticles (NPs), with sizes ranging from 4 to 40 nm, to cell culture media containing 10% of fetal bovine serum. Under in vitro cell culture conditions, zeta potential measurements, UV-vis spectroscopy, dynamic light scattering and transmission electron microscope analysis were used to monitor the time evolution of the inorganic NP-protein corona formation and to characterize the stability of the NPs and their surface state at every stage of the experiment. As expected, the red-shift of the surface plasmon resonance peak, as well as the drop of surface charge and the increase of the hydrodynamic diameter indicated the conjugation of proteins to NPs. Remarkably, an evolution from a loosely attached toward an irreversible attached protein corona over time was observed. Mass spectrometry of the digested protein corona revealed albumin as the most abundant component which suggests an improved biocompatibility.

Murine bone marrow macrophages were able to recognize gold nanoparticle peptide conjugates, while peptides or nanoparticles alone were not recognized. Consequently, in the presence of conjugates, macrophage proliferation was stopped and pro-inflammatory cytokines such as TNF-alpha, IL-1beta, and IL-6, as well as nitric oxide synthase (NOS2) were induced. Furthermore, macrophage activation by gold nanoparticles conjugated to different peptides appeared to be rather independent of peptide length and polarity, but dependent on peptide pattern at the nanoparticle surface. Correspondingly, the biochemical type of response also depended on the type of conjugated peptide and could be correlated with the degree of ordering in the peptide coating. These findings help to illustrate the basic requirements involved in medical nanoparticle conjugate design to either activate the immune system or hide from it in order to reach their targets before being removed by phagocytes.