Functionalized graphene-coated cobalt nanoparticles for highly efficient surface-assisted laser desorption/ionization mass spectrometry analysis.

Graphene-coated cobalt nanoparticles surface-functionalized with benzylamine groups (CoC-NH(2) nanomagnets) were shown to effectively enrich analytes for surface-assisted laser desorption/ionization mass spectrometry (affinity SALDI-MS) analysis. These CoC-NH(2) nanomagnets are highly suited for use with affinity SALDI-MS because their mean diameter of 30 nm, high specific surface area of 15 m(2) g(-1), and high-strength saturation magnetization of 158 emu g(-1) led to efficient extraction of analytes by magnetic separation, which in turn enabled excellent SALDI-MS performance. Surface modification of CoC nanomagnets with benzylamine groups increased the yield of peptide ions and decreased fragmentation of benzylpyridinium ions, so-called "thermometer ions" formed through soft ionization. The CoC-NH(2) nanomagnets were used to extract perfluorooctanesulfonate from large volumes of aqueous solutions by magnetic separation, which was identified directly by SALDI-MS analysis with high sensitivity even at the sub-part-per-trillion level (∼0.1 ng/L). The applicability of CoC-NH(2) nanomagnets in conjunction with SALDI-MS for the enrichment and detection of pentachlorophenol, bisphenol A, and polyfluorinated compounds (PFCs) with varying chain length, which are environmentally significant compounds, as well as small drugs, was also evaluated.

Physical defect formation in few layer graphene-like carbon on metals: influence of temperature, acidity, and chemical functionalization.

A systematical examination of the chemical stability of cobalt metal nanomagnets with a graphene-like carbon coating is used to study the otherwise rather elusive formation of nanometer-sized physical defects in few layer graphene as a result of acid treatments. We therefore first exposed the core-shell nanomaterial to well-controlled solutions of altering acidity and temperature. The release of cobalt into these solutions over time offered a simple tool to monitor the progress of particle degradation. The results suggested that the oxidative damage of the graphene-like coatings was the rate-limiting step during particle degradation since only fully intact or entirely emptied carbon shells were found after the experiments. If ionic noble metal species were additionally present in the acidic solutions, the noble metal was found to reduce on the surface of specific, defective particles. The altered electrochemical gradients across the carbon shells were however not found to lead to a faster release of cobalt from the particles. The suggested mechanistic insight was further confirmed by the covalent chemical functionalization of the particle surface with chemically inert aryl species, which leads to an additional thickening of the shells. This leads to reduced cobalt release rates as well as slower noble metal reduction rates depending on the augmentation of the shell thickness.

Iron core/shell nanoparticles as magnetic drug carriers: possible interactions with the vascular compartment.

AIMS: Nanomagnets with metal cores have recently been shown to be promising candidates for magnetic drug delivery due to higher magnetic moments compared with commonly used metal oxides. Successful application strongly relies on a safe implementation that goes along with detailed knowledge of interactions and effects that nanomagnets might impart once entering the body. MATERIALS & METHODS: In this work, we put a particular focus on the interactions of ultra-strong metal nanomagnets (≥ three-times higher in magnetization compared with oxide nanoparticles) within the vascular compartment. Individual aspects of possible effects are addressed, including interactions with the coagulation cascade, the complement system, phagocytes and toxic or inflammatory reactions both by blood and endothelial cells in response to nanomagnet exposure. RESULTS: We show that carbon-coated metal nanomagnets are well-tolerated by cells of the vascular compartment and have only minor effects on blood coagulation. CONCLUSION: These findings provide the fundament to initiate successful first in vivo evaluations opening metal nanomagnets with improved magnetic properties to fascinating applications in nanomedicine.

Immobilized ß-cyclodextrin on surface-modified carbon-coated cobalt nanomagnets: reversible organic contaminant adsorption and enrichment from water.

Surface-modified magnetic nanoparticles can be used in extraction processes as they readily disperse in common solvents and combine high saturation magnetization with excellent accessibility. Reversible and recyclable adsorption and desorption through solvent changes and magnetic separation provide technically attractive alternatives to classical solvent extraction. Thin polymer layered carbon-coated cobalt nanoparticles were tagged with ß-cyclodextrin. The resulting material reversibly adsorbed organic contaminants in water within minutes. Isolation of the immobilized inclusion complex was easily carried out within seconds by magnetic separation due to the strong magnetization of the nanomagnets (metal core instead of hitherto used iron oxide). The trapped molecules were fully and rapidly recovered by filling the cyclodextrin cavity with a microbiologically well accepted substitute, e.g., benzyl alcohol. Phenolphthalein was used as a model compound for organic contaminants such as polychlorinated dibenzodioxins (PCDDs) or bisphenol A (BPA). Fast regeneration of nanomagnets (compared to similar cyclodextrin-based systems) under mild conditions resulted in 16 repetitive cycles (adsorption/desorption) at full efficiency. The high removal and regeneration efficiency was examined by UV-vis measurements at chemical equilibrium conditions and under rapid cycling (5 min). Experiments at ultralow concentrations (160 ppb) underline the high potential of cyclodextrin modified nanomagnets as a fast, recyclable extraction method for organic contaminants in large water streams or as an enrichment tool for analytics.

Nanoparticle cytotoxicity depends on intracellular solubility: comparison of stabilized copper metal and degradable copper oxide nanoparticles.

Metal nanoparticles have distinctly different chemical and physical properties than currently investigated oxides. Since pure metallic nanoparticles are igniting at air, carbon stabilized copper nanoparticles were used as representative material for this class. Using copper as a representative example, we compare the cytotoxicity of copper metal nanoparticles stabilized by a carbon layer to copper oxide nanoparticles using two different cell lines. Keeping the copper exposure dose constant, the two forms of copper showed a distinctly different response. Whilst copper oxide had already been reported to be highly cytotoxic, carbon-coated copper nanoparticles were much less cytotoxic and more tolerated. Measuring the two material's intra- and extracellular solubility in model buffers explained this difference on the basis of altered copper release when supplying copper metal or the corresponding oxide particles to the cells. Control experiments using pure carbon nanoparticles were used to exclude significant surface effects. Reference experiments with ionic copper solutions confirmed a similar response of cultures if exposed to copper oxide nanoparticles or ionic copper. These observations are in line with a Trojan horse-type mechanism and illustrate the dominating influence of physico-chemical parameters on the cytotoxicity of a given metal.

Magnetic EDTA: coupling heavy metal chelators to metal nanomagnets for rapid removal of cadmium, lead and copper from contaminated water.

Attachment of EDTA-like chelators to carbon coated metal nanomagnets results in a magnetic reagent for the rapid removal of heavy metals from solutions or contaminated water by three orders of magnitude to concentrations as low as microg L(-1).

Graphene-stabilized copper nanoparticles as an air-stable substitute for silver and gold in low-cost ink-jet printable electronics.

Metallic copper nanoparticles were synthesized by a bottom-up approach, and in situ coated with protective shells of graphene in order to get a metal nanopowder of high air stability and chemical inertness. Using an amphiphilic surfactant, a water-based copper nanocolloid could be prepared and successfully printed onto a polymer substrate by conventional ink-jet printing using household printers. The dried printed patterns exhibited strong metallic gloss and an electrical conductivity of >1 S cm(-1) without the need for a sintering or densification step. This conductivity currently limits use in electronics to low current application or shielding and decorative effects. The high stability of graphene-coated copper nanoparticles makes them economically a most attractive alternative to silver or gold nanocolloids, and will strongly facilitate the industrial use of metal nanocolloids in consumer goods.

Highly sensitive optical detection of humidity on polymer/metal nanoparticle hybrid films.

Porous metal films for optical humidity sensing were prepared from copper nanoparticles protected by a 2-3 nm carbon coating, a silicon tenside, and a polymeric wetting agent. Exposure to water or solvent vapor revealed an exceptional sensitivity with optical shifts in the visible light range of up to 50 nm for a change of 1% in relative humidity. These properties could be attributed to a combination of surface plasmon resonance effects at low humidity and thin film interference at higher water or solvent concentration in the surrounding air. The simple concept and use of ultra-low-cost materials suggests application of such porous metal-film-based optical humidity sensors in large-scale applications for food handling, storage, and transport.