The femtosecond laser ablation of a gold target in aqueous solutions has been used to produce colloidal Au nanoparticles with controlled surface chemistry. A detailed chemical analysis showed that the nanoparticles formed were partially oxidized by the oxygen present in solution. The hydroxylation of these Au-O compounds, followed by a proton loss to give surface Au-O -, resulted in the negative charging of the nanoparticles. The partial oxidation of the gold nanoparticle surface enhances its chemical reactivity and consequently has a strong impact on its growth. In particular, the oxidized surface reacted efficiently with Cland OHto augment its net surface charge. This limited the coalescence of the particles, due to electrostatic repulsion, and led to a significant reduction of their size. Taking advantage of the repulsion effect, efficient size control was achieved using different salts (7 ( 5 nm for 10 mM KCl, 5.5 ( 4 nm for 10 mM NaCl, 8 ( 5 nm for NaOH, pH 9.4), a considerable improvement comparatively to particles prepared in deionized water, using identical ablation conditions, where particles of 1-250 nm were produced. The partially oxidized gold surface was also suitable for surface modification through both covalent and electrostatic interactions during particle formation. Using solutions of N-propylamine, we showed an efficient control of nanoparticle size (5-8 ( 4-7 nm) by the involvement of these interactions. The results obtained help to develop methodologies for the control of laser-ablation-based nanoparticle growth and the functionalization of nanoparticle surfaces by specific interactions.

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We use high purity Fe oxide nanoparticles to confirm the Fe 2p X-ray photoemission peak attributions made in our previous study of Fe nanoparticles and the initial stage of their oxidation. To accomplish this, we have found it necessary to consider the spectral contributions of the ligand field of the Fe−O crystal structure, the crystalline disorder at the nanoparticle surface, and the Russell−Saunders broadening of the FeIII components of the Fe 2p spectra.

The aim of the present study was to evaluate the cellular interaction of nanoparticles (NPs) prepared from different pegylated polymers and elucidate the effect of polymer architecture, for instance, grafted versus block copolymer on their cellular uptake. Fluorescein-labeled NPs of four different polymers, viz., poly(D,L-lactide) (PLA), poly(ethylene glycol)(1%)-graft-poly(D,L-lactide) (PEG(1%)-g-PLA), poly(ethylene glycol)(5%)-graft-poly(D,L-lactide) (PEG(5%)-g-PLA), and (poly(D,L-lactide)-block-poly(ethylene glycol)-block-poly(D,L-lactide))(n) multiblock copolymer (PLA-PEG-PLA)(n) were prepared. These NPs were characterized for their size, zeta-potential, and surface morphology. XPS studies revealed possibility of chemical interaction between PLA-COOH groups and PVA-OH groups, thus making it difficult to be washed off the NP surface completely. Grafted polymer NPs showed more surface PEG coverage than (PLA-PEG-PLA)(n) despite of their comparatively lower PEG content. The results of surface properties were translated into protein binding showing least amount of proteins bound to grafted copolymer NPs as against multiblock copolymer NPs. NPs showed no toxicity to RAW 264.7 cells. Cellular uptake of NPs was temperature and concentration-dependent as well as involved clathrin-mediated processes. Thus, this study confirms the importance of polymer architecture in determining the surface properties and hence, protein binding and cellular interactions of NPs. Also, it was shown that grafted copolymer NPs reduced macrophage uptake as compared to multiblock copolymer although mechanisms different than phagocytosis were involved.

A tetrahedral model is presented to explain the bonding properties of nonstoichiometric amorphous silicon oxynitride (a-SiOxNy) alloys, grown under highly nonequilibrium conditions, whose structures obey neither the random bonding model nor the random mixture model. Based on our approach, a numerical procedure is proposed to obtain the relative atomic percentages of each component structural phase from the deconvolution of the high-resolution x-ray photoelectron spectroscopy (XPS) spectra in the Si 2p3∕2 region. The tetrahedral model is then used to study the bonding properties of a-SiOxNy films grown by electron-cyclotron resonance plasma-enhanced chemical-vapor deposition, having relatively low values of the O/Si atomic ratio (⩽0.37) incorporated in their networks. The experimental results show that five tetrahedral phases (tetrahedrons Si–Si4, Si–Si2ON, Si–N4, Si–Si3O, and Si–O4) are present in a-SiOxNy films with low N/Si atomic ratios (⩽0.93), while only three phases (Si–SiON2, Si–N4, and Si–O2N2) are present in samples with higher N/Si atomic ratios (⩾1.12). The Si3N4 phase is the most important bonding unit and it is the only phase present in all our samples. These results are corroborated by survey scans and by comparison with the high-resolution XPS spectra in the N 1s region. They support the validity of the model proposed for a-SiOxNy alloys and the XPS analysis, correlated with growth conditions, presented in this work.

Eumelanin is a ubiquitous pigment in the human body, animals, and plants, with potential for bioelectronic applications because of its unique set of physical and chemical properties, including strong UV‐vis absorption, mixed ionic/electronic conduction, free radical scavenging and anti‐oxidant properties. Herein, a detailed investigation is reported of eumelanin thin films grown on substrates patterned with gold electrodes as a model system for device integration, using electrical measurements, atomic force microscopy, scanning electron microscopy, fluorescence microscopy, and time‐of‐flight secondary ion mass spectroscopy. Under prolonged electrical biasing in humid air, one can observe gold dissolution and formation of gold‐eumelanin nanoaggregates, the assembly of which leads to the formation of dendrites forming conductive pathways between the electrodes. Based on results collected with eumelanins from different sources, a mechanism is proposed for the formation of the nanoaggregates and dendrites, taking into account the metal binding properties of eumelanin. The surprising interaction between eumelanin and gold points to new opportunities for the fabrication of eumelanin‐gold nanostructures and biocompatible memory devices and should be taken into account in the design of devices based on eumelanin thin films.

The nature of the reduction agent changes drastically the palladium nanomaterials chemical stability, which subsequently alters earnestly their catalytic performances.

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