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.
The noble metal nanoparticles of Pd, Au, and Ag embedded in the shell layer of core-shell poly(styreneco-4-vinylpyridine) micospheres were synthesized, and the catalytic activity of the shell-embedded Pd nanoparticles was investigated. To increase the accessible active site and therefore increase the catalytic activity of noble metal nanoparticles, the in situ synthesized noble metal nanoparticles are selectively immobilized in the outer shell layer of the core-shell poly(styrene-co-4-vinylpyridine) microspheres, which are synthesized by one-stage soap-free emulsion polymerization in water and contain a core of polystyrene and a coordinative shell of poly(4-vinylpyridine). It is found the Pd nanoparticles embedded in the shell layer of the core-shell micospheres are an efficient and easily reusable catalyst for Suzuki reactions performed in water.
The single-crystal structure of [Au 9 (PPh 3 ) 8 ](NO 3 ) 3 was resolved for the first time with atomic resolution. The cluster has crystallographic D 2 and approximate molecular D 2h skeletal symmetry derived from an icosahedron. Voltammetry of the Au 9 clusters in CH 2 Cl 2 reveals a 1.78-eV energy gap between the first one-electron oxidation peak and the first re-
Blending high-permittivity (εr) ceramic powders or conductive fillers into polymers to form 0-3-type composites has been regarded as one of the most promising processes to achieve high-dielectric-permittivity materials with excellent processing performance. The high dielectric loss and conductivity induced by the interface between the matrix and fillers as well as the leakage current have long been a great challenge of dielectric composites, and the resolution of these challenges is still an open question. In this work, poly(vinylidenefluoride-trifluorethylene with double bonds)/graphene nanosheets (P(VDF-TrFE-DB)/GNS) terpolymer nanocomposites were fabricated via a solution-cast process. GNSs were functionalized with KH550 to improve the dispersion in the terpolymer matrix solution and crosslinked with P(VDF-TrFE-DB) by a free-radical addition reaction in the nanocomposites. Compared with neat terpolymer, significantly increased dielectric permittivity and a low loss were observed for the composites. For instance, at 1 kHz the P(VDF-TrFE-DB)/GNS composites with 4 vol % GNS possessed a dielectric permittivity of 74, which is over seven times larger than that of neat terpolymer. However, a rather low dielectric loss (0.08 at 1 kHz) and conductivity (3.47 × 10(-7) S/m at 1 kHz) are observed in the P(VDF-TrFE-DB)/GNS composites containing up to 12 vol % GNS. The covalent bonding constructed between P(VDF-TrFE-DB) and GNS is responsible for the reduced aspect ratio of the GNS and the crystalline properties of P(VDF-TrFE-DB) as well as the improved compatibility between them. As a result, the high-dielectric-loss conductivity of polymer composites, mainly induced by conduction loss and the interface polarization between the matrix and filler, were effectively restricted. Meanwhile, the 3D network established between P(VDF-TrFE-DB) and GNS endows the P(VDF-TrFE-DB)/GNS composites at high temperature with excellent mechanical and dielectric properties. Besides preparing high-performance dielectric composites, this facile route may also be utilized to fabricate high-performance nanocomposites by inhibiting the poor compatibility between fillers and polymeric matrix.
A method of one‐stage soap‐free emulsion polymerization to synthesize narrowly dispersed core‐shell microspheres is proposed. Following this method, core‐shell microspheres of poly(styrene‐co‐4‐vinylpyridine), poly(styrene‐co‐methyl acrylic acid), and poly[styrene‐co‐2‐(acetoacetoxy)ethyl methacrylate‐co‐methyl acrylic acid] are synthesized by one‐stage soap‐free emulsion polymerization of a mixture of one or two hydrophobic monomers and a suitable hydrophilic monomer in water. The effect of the molar ratio of the hydrophobic monomer to the hydrophilic one on the size, the core thickness, and the shell thickness of the core‐shell microspheres is discussed. The molar ratio of the hydrophobic and hydrophilic monomers and the hydrophilicity of the resultant oligomers of the hydrophilic monomer are optimized to synthesize narrowly dispersed core‐shell microspheres. A possible mechanism of one‐stage soap‐free emulsion polymerization to synthesize core‐shell microspheres is suggested and coagglutination of the oligomers of the hydrophilic monomers on the hydrophobic core is considered to be the key to form core‐shell microspheres. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1192–1202, 2008
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