Gold nanoparticles are widely used in biomedical imaging and diagnostic tests. Based on their established use in the laboratory and the chemical stability of Au(0), gold nanoparticles were expected to be safe. The recent literature, however, contains conflicting data regarding the cytotoxicity of gold nanoparticles. Against this background a systematic study of water-soluble gold nanoparticles stabilized by triphenylphosphine derivatives ranging in size from 0.8 to 15 nm is made. The cytotoxicity of these particles in four cell lines representing major functional cell types with barrier and phagocyte function are tested. Connective tissue fibroblasts, epithelial cells, macrophages, and melanoma cells prove most sensitive to gold particles 1.4 nm in size, which results in IC(50) values ranging from 30 to 56 microM depending on the particular 1.4-nm Au compound-cell line combination. In contrast, gold particles 15 nm in size and Tauredon (gold thiomalate) are nontoxic at up to 60-fold and 100-fold higher concentrations, respectively. The cellular response is size dependent, in that 1.4-nm particles cause predominantly rapid cell death by necrosis within 12 h while closely related particles 1.2 nm in diameter effect predominantly programmed cell death by apoptosis.
We have fabricated pentacene organic thin film transistors with spin-coated polymer gate dielectric layers, including cross-linked polyvinylphenol and a polyvinylphenol-based copolymer, and obtained devices with excellent electrical characteristics, including carrier mobility as large as 3 cm2/V s, subthreshold swing as low as 1.2 V/decade, and on/off current ratio of 105. For comparison, we have also fabricated pentacene transistors using thermally grown silicon dioxide as the gate dielectric and obtained carrier mobilities as large as 1 cm2/V s and subthreshold swing as low as 0.5 V/decade.
Organic thin film transistors (TFTs) are of interest for a variety of large-area electronic applications, such as displays, sensors and electronic barcodes. One of the key problems with existing organic TFTs is their large operating voltage, which often exceeds 20 V. This is due to poor capacitive coupling through relatively thick gate dielectric layers: these dielectrics are usually either inorganic oxides or nitrides, or insulating polymers, and are often thicker than 100 nm to minimize gate leakage currents. Here we demonstrate a manufacturing process for TFTs with a 2.5-nm-thick molecular self-assembled monolayer (SAM) gate dielectric and a high-mobility organic semiconductor (pentacene). These TFTs operate with supply voltages of less than 2 V, yet have gate currents that are lower than those of advanced silicon field-effect transistors with SiO2 dielectrics. These results should therefore increase the prospects of using organic TFTs in low-power applications (such as portable devices). Moreover, molecular SAMs may even be of interest for advanced silicon transistors where the continued reduction in dielectric thickness leads to ever greater gate leakage and power dissipation.
Gold nanoparticles (AuNPs) are generally considered nontoxic, similar to bulk gold, which is inert and biocompatible. AuNPs of diameter 1.4 nm capped with triphenylphosphine monosulfonate (TPPMS), Au1.4MS, are much more cytotoxic than 15-nm nanoparticles (Au15MS) of similar chemical composition. Here, major cell-death pathways are studied and it is determined that the cytotoxicity is caused by oxidative stress. Indicators of oxidative stress, reactive oxygen species (ROS), mitochondrial potential and integrity, and mitochondrial substrate reduction are all compromised. Genome-wide expression profiling using DNA gene arrays indicates robust upregulation of stress-related genes after 6 and 12 h of incubation with a 2 x IC50 concentration of Au1.4MS but not with Au15MS nanoparticles. The caspase inhibitor Z-VAD-fmk does not rescue the cells, which suggests that necrosis, not apoptosis, is the predominant pathway at this concentration. Pretreatment of the nanoparticles with reducing agents/antioxidants N-acetylcysteine, glutathione, and TPPMS reduces the toxicity of Au1.4MS. AuNPs of similar size but capped with glutathione (Au1.1GSH) likewise do not induce oxidative stress. Besides the size dependency of AuNP toxicity, ligand chemistry is a critical parameter determining the degree of cytotoxicity. AuNP exposure most likely causes oxidative stress that is amplified by mitochondrial damage. Au1.4MS nanoparticle cytotoxicity is associated with oxidative stress, endogenous ROS production, and depletion of the intracellular antioxidant pool.
Gold nanoparticles (GNP) provide many opportunities in imaging, diagnostics, and therapies of nanomedicine. Hence, their biokinetics in the body are prerequisites for specific tailoring of nanomedicinal applications and for a comprehensive risk assessment.We administered 198 Au-radio-labelled monodisperse, negatively charged GNP of five different sizes (1.4, 5, 18, 80, 200nm) and 2.8nm GNP with opposite surface charges by intravenous injection into rats. After 24 h the biodistribution of the GNP was quantitatively measured by gamma-spectrometry.The size and surface charge of GNP strongly determine the biodistribution. Most GNP accumulated in the liver increased from 50% of 1.4nm GNP to > 99% of 200nm GNP. In contrast, there was little size dependent accumulation of 18nm to 200nm GNP in most other organs. However, for GNP between 1.4nm and 5nm the accumulation increased sharply with decreasing size; i.e. a linear increase with the volumetric specific surface area. The differently charged 2.8nm GNP led to significantly different accumulations in several organs.We conclude that the alterations of accumulation in the various organs and tissues, depending on GNP size and surface charge, are mediated by dynamic protein binding and exchange. A better understanding of these mechanisms will improve drug delivery and dose estimates used in risk assessment.
1.4‐nm gold nanoparticles (NPs) are observed to cross the air/blood barrier of the lungs much more efficiently than 18‐nm gold NPs (see figure). The NP accumulation pattern in the secondary‐target organs differs strongly from those seen after direct intravenous injection. From this, it is hypothesized that NPs interact dynamically with proteins and cells, which determines their accumulation in the various organs.
Gold nanoparticles ranging in diameter from 1 to 8 nanometers were prepared on top of silicon wafers in order to study the size dependence of their oxidation behavior when exposed to atomic oxygen. X-ray photoelectron spectroscopy showed a maximum oxidation resistance for "magic-number" clusters containing 55 gold atoms. This inertness is not related to electron confinement leading to a size-induced metal-to-insulator transition, but rather seems to be linked to the closed-shell structure of such magic clusters. The result additionally suggests that gold-55 clusters may act as especially effective oxidation catalysts, such as for oxidizing carbon monoxide.
Die Reduktion von C6H5)3PAuCl mit B2H6 in Benzol ergibt Au9,2[P(C6H5)3]2Cl, das mittels Molmassebestimmungen als Au55[P(C6H5)3]12Cl6 charakterisiert wurde. Ein einfaches Modell, beruhend auf einer Anordnung dichtest gepackter Goldatome, führt zu einem Goldcluster, dessen Aufbau mit der ungewöhnlichen chemischen Zusammensetzung in guter Übereinstimmung ist. Das Mößbauer‐Spektrum der Verbindung zeigt vier Sorten von Goldatomen: einen metallischen Anteil (Au13‐Kern), durch P(C6H5)3‐bzw. Cl‐Liganden Koordinierte Au‐Atome, sowie unkoordi‐niertes Oberflächengold. Mit Brom und lod läß sich der Komplex zu (C6H5)3PAuCl, (C6H5)3 PAuBr(I) und metallischem Gold abbauen. Die Thermolyse bei 50°C führt quantitativ zu [(C6H5)3P]2AuCl und Gold.
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