Evaluation of Functional SiO2 Nanoparticles Toxicity by a 3D Culture Model.

CONTEXT: as a kind of non-metal oxide SiO2 NPs have been extensively used in biomedicine, pharmaceuticals and other industrial manufacturing fields, such as DNA delivery, cancer therapy… Our group had developed a method based on microemulsion process to prepare SiO2 NPs incorporating photonic or magnetic nanocrystals and luminescent nanosized inorganic metal atom clusters. However, the toxicity of nanoparticles is known to be closely related to their physico-chemical characteristics and chemical composition. OBJECT: it is therefore of interest to investigate the toxicity of these novel SiO2 NPs to the cells that may come in contact. MATERIALS AND METHODS: the potential toxic effect of the functional @SiO2 NPs containing Mo6 clusters with or without gold nanoparticles was investigated, at concentrations 1 µg/mL, 10 µg/mL and 100 µg/mL each, on three different cell lines. Cell viability was measured by the MTT test in monolayer's culture whereas the cytotoxicity in spheroid model was examined by the APH assay. In a second time, oxidative-stress-induced cytotoxicity was investigated through glutathione levels dosages. RESULTS: the results indicated that both A549 and L929 cell lines did not exhibit susceptibility to functional @SiO2 NPs-induced oxidative stress unlike KB cells. DISCUSSION: SiO2 NPs containing CMB may become toxic to cultured cells but only at a very high dosage level. Therefore, this toxicity depends on cell lines and more, on the model of cell cultures. The selection of appropriate cell line remains a critical component in nanotoxicology. CONCLUSION: these results are relevant to future applications of SiO2 gold-cluster NPs in controlled release applications.

Multifunctional hybrid silica nanoparticles based on [Mo6Br14]²â» phosphorescent nanosized clusters, magnetic γ-Fe2O3 and plasmonic gold nanoparticles.

We report on the synthesis, characterization and photophysical study of new luminescent and magnetic hybrid silica nanoparticles. Our method is based on the co-encapsulation of single maghemite γ-Fe2O3 nanoparticles and luminescent molybdenum cluster units [Mo6Br(i)8Br(a)6](2-) through a water-in-oil (W/O) microemulsion technique. The as-prepared core-shell [Cs2Mo6Br14-γFe2O3]@SiO2 nanoparticles (45-53 nm) possess a single magnetic core (6, 10.5 or 15 nm) and the cluster units are dispersed in the entire volume of the silica sphere. The [Cs2Mo6Br14-γFe2O3]@SiO2 nanoparticles have a perfect spherical shape with a good monodispersity and they display red and near-infrared (NIR) emission in water under UV excitation, whose intensity depends on the magnetic core size. The hybrid nanoparticles have been characterized by transmission electron microscopy (TEM), high annular angular dark field scanning transmission electron microscopy (HAADF-STEM), energy-dispersive X-ray spectroscopy (EDX), UV-Vis-NIR spectroscopy and magnetometer SQUID analysis. Small gold nanoparticles were successfully nucleated at the surface of the hybrid silica nanoparticles in order to add plasmonic properties.

Rational design of the gram-scale synthesis of nearly monodisperse semiconductor nanocrystals.

We address two aspects of general interest for the chemical synthesis of colloidal semiconductor nanocrystals: (1) the rational design of the synthesis protocol aiming at the optimization of the reaction parameters in a minimum number of experiments; (2) the transfer of the procedure to the gram scale, while maintaining a low size distribution and maximizing the reaction yield. Concerning the first point, the design-of-experiment (DOE) method has been applied to the synthesis of colloidal CdSe nanocrystals. We demonstrate that 16 experiments, analyzed by means of a Taguchi L16 table, are sufficient to optimize the reaction parameters for controlling the mean size of the nanocrystals in a large range while keeping the size distribution narrow (5-10%). The DOE method strongly reduces the number of experiments necessary for the optimization as compared to trial-and-error approaches. Furthermore, the Taguchi table analysis reveals the degree of influence of each reaction parameter investigated (e.g., the nature and concentration of reagents, the solvent, the reaction temperature) and indicates the interactions between them. On the basis of these results, the synthesis has been scaled up by a factor of 20. Using a 2-L batch reactor combined with a high-throughput peristaltic pump, different-sized samples of CdSe nanocrystals with yields of 2-3 g per synthesis have been produced without sacrificing the narrow size distribution. In a similar setup, the gram-scale synthesis of CdSe/CdS/ZnS core/shell/shell nanocrystals exhibiting a fluorescence quantum yield of 81% and excellent resistance of the photoluminescence in presence of a fluorescent quencher (aromatic thiol) has been achieved.PACS: 81.20.Ka, 81.07.Bc, 78.67.Bf.

[Mesoporous silica nanoparticles for two-photon fluorescence]. / Nanoparticules de silice mésoporeuse optimisées pour la fluorescence à deux photons.

Mesoporous silica nanoparticles have unique properties: a specific large surface or a narrow casting of the sizes of pores. The perspectives of use are the creation of new tools for the premature diagnosis. For these potential biological applications, the harmlessness of these nanoparticles must be established.

Quenching of molecular fluorescence on the surface of monolayer-protected gold nanoparticles investigated using place exchange equilibria.

The insertion of fluorescently labeled thiols into the protecting self-assembled monolayer on the surface of gold nanoparticles through place exchange reactions and the effects of this insertion on the photophysical properties of the fluorophores are investigated. Analysis of solution-phase fluorescence data using a dynamic equilibrium model yields the equilibrium constant for the place exchange equilibrium, as well as the relative fluorescence brightness of the fluorophores on the particle surface. In all cases we find a significant quenching of the fluorescence, and potential reasons for this quenching are discussed. In the case of these relatively small particles (4.5 nm diameter), the quenching appears to be mainly related to enhanced nonradiative deactivation pathways. The place exchange equilibrium constant reveals a reduced affinity of the fluorescently labeled thiols for insertion into the nonfluorescent alkylthiol monolayer (K(eq) approximately 0.2) compared to unlabeled alkylthiols.

Distance-dependent fluorescence quenching on gold nanoparticles ensheathed with layer-by-layer assembled polyelectrolytes.

We report on the preparation, characterization, and photophysical study of new fluorescent core/shell nanoparticles fabricated by electrostatic layer-by-layer assembly. On the basis of gold cores with a diameter of 13 nm, these nanocolloids possess different fluorescently labeled polymer corona layers at various distances from the surface of the core metal using nonfluorescent polyelectrolytes as spacer layers. UV-visible spectroscopy and transmission electron microscopy confirm that the particle suspensions of fluorescently labeled core/shell nanoparticles are stable at all stages of their construction. Photophysical investigations reveal strongly distance-dependent fluorescence quenching in these particle systems. The contribution of the metal core to this quenching can be assesed precisely after the gentle dissolution of the gold cores by potassium cyanide. The photophysical measurements reveal clearly that the gold nanoparticles decrease the transition probability for radiative transitions.

Action cross sections of two-photon excited luminescence of some Eu(III) and Tb(III) complexes.

Four different luminescent lanthanide complexes have been studied with respect to multiphoton excitation using near-infrared femtosecond pulses. The method for measuring action cross sections of two-photon excited fluorescence in solution relative to a known standard is reviewed. Two refractive index-related corrections are necessary in this method: one for the multiphoton excitation process, the other for the collection of the emitted light. It has been found that (2,4,6-trimethoxyphenyl)dipicolinic acid and Michler's ketone are reasonable sensitisers of two-photon excited lanthanide luminescence in solution, whereas dipicolinic acid and carbostyril-124 do not give rise to any detectable two-photon excited lanthanide luminescence using modest excitation powers (<20 mW focused at the sample) in the 700-1000 nm range.