Carbon nanotubes randomly decorated with gold clusters: from nano2hybrid atomic structures to gas sensing prototypes.

Carbon nanotube surfaces, activated and randomly decorated with metal nanoclusters, have been studied in uniquely combined theoretical and experimental approaches as prototypes for molecular recognition. The key concept is to shape metallic clusters that donate or accept a fractional charge upon adsorption of a target molecule, and modify the electron transport in the nanotube. The present work focuses on a simple system, carbon nanotubes with gold clusters. The nature of the gold-nanotube interaction is studied using first-principles techniques. The numerical simulations predict the binding and diffusion energies of gold atoms at the tube surface, including realistic atomic models for defects potentially present at the nanotube surface. The atomic structure of the gold nanoclusters and their effect on the intrinsic electronic quantum transport properties of the nanotube are also predicted. Experimentally, multi-wall CNTs are decorated with gold clusters using (1) vacuum evaporation, after activation with an RF oxygen plasma and (2) colloid solution injected into an RF atmospheric plasma; the hybrid systems are accurately characterized using XPS and TEM techniques. The response of gas sensors based on these nano(2)hybrids is quantified for the detection of toxic species like NO(2), CO, C(2)H(5)OH and C(2)H(4).

Uptake visualization of deltamethrin by NanoSIMS and acute toxicity to the water flea Daphnia magna.

The objective of this study was to investigate the uptake of deltamethrin, an insecticide, by Daphnia magna neonates by SIMS and to compare these findings with results based on established toxicity tests. Young daphnids (aged <24 h) were exposed to 0, 50 and 200 microg L(-1) (ppb) deltamethrin. Mobile, immobile and dead animals were enumerated after 24 and 48 h following OECD 202 [OECD 202, 2004. Daphnia sp., acute immobilisation test, guideline for testing of chemicals] guidelines. The animals were embedded in epoxy resin, cut into semi-thin sections (500 nm) and placed on silicon supporters. NanoSIMS 50 (Cameca) images were made from tissues of the intestine for carbon, nitrogen (measured as CN), phosphorus and bromine. To distinguish between relative concentrations of bromine in the guts from different exposure concentrations of deltamethrin, a carbon normalization method was carried out. Both deltamethrin concentrations and time showed a significant effect on immobilization and mortality of the daphnids (P<0.0001). Bromine from deltamethrin could be visualized by NanoSIMS in all exposed gut tissues (gut wall, microvilli layer, perithropic membrane). Highest deltamethrin concentrations following (12)C normalization were found in animals exposed to 200 microg L(-1) deltamethrin, followed by 50 microg L(-1) and the control. NanoSIMS 50 was successfully used as a supplemental technique for elucidating the relation between the uptake and localization of deltamethrin and its toxicity to D. magna. These results highlight the potential usefulness of NanoSIMS to detect marker elements of xenobiotic compounds within exposed organisms, to compare relative exposure concentrations, and to locate these compounds at their original tissue location.

NanoSIMS 50 elucidation of the natural element composition in structures of cyanobacteria and their exposure to halogen compounds.

AIMS: NanoSIMS (secondary ion mass spectrometry) is a powerful technique for mapping the elemental composition of a variety of small-scale samples (e.g. in Material Research, Cosmochemistry and Geology). However, its analytical features are making it also valuable to address biological questions. We demonstrate the ability of the NanoSIMS 50 to map elements at subcellular lateral resolution (approx. 50 nm) within cyanobacteria (Anabaena sp. and Cylindrospermum alatosporum) and its feasibility to investigate the uptake of bromine-containing substances (NaBr and deltamethrin). METHODS AND RESULTS: Elemental maps of O, N, P and S were obtained from semi-thin sections of different cell types (chemically fixed and resin-embedded heterocysts, akinetes and vegetative cells). NanoSIMS enabled the detection of various characteristic cell sub-structures and inclusions. A homogenous bromine distribution was detected following NaBr and deltamethrin exposure, at Br-concentrations of 0.05, 0.5 (NaBr) and 0.0025 mmol l(-1) (deltamethrin). CONCLUSIONS: NanoSIMS allowed study of the mapping of common elements in cyanobacterial cells and the uptake of NaBr and deltamethrin. SIGNIFICANCE AND IMPACT OF THE STUDY: These results highlight the potential usefulness of NanoSIMS analysis for tracking elements within cell structures at the nanoscale and the ability to detect marker elements of xenobiotic compounds within exposed organisms.

Secondary ion and laser ablation mass spectrometry for the quantitative characterization of styrene-butadiene copolymers.

Styrene-butadiene copolymers were analyzed by static secondary ion mass spectrometry (S-SIMS) and laser ablation Fourier transform ion cyclotron resonance mass spectrometry (LA-FTICRMS) to obtain quantitative information based on specific ions. Silver deposition was performed on polystyrene, butadiene rubber and styrene-butadiene rubber. Under these experimental conditions, new secondary ions were detected, in particular silver-cationized butadiene [M(butadiene) - Ag](+) and styrene [M(styrene) - Ag](+) monomers. In contrast, LA-FTICRMS experiments did not require pretreatment. At high laser power density, UV photons (193, 266 and 355 nm) allowed the detection of styrene and butadiene monomers at m/z 104 and 54, respectively. The use of the observed ions by SIMS or LA-FTICRMS ensures that quantitative information on the relative distribution of each monomer is obtained. However, the silver coating thickness in the SIMS experiment seems to have an important influence on the quantitative information obtained. For LA-FTICRMS experiments, the best results are obtained at a wavelength of 355 nm.