A comparative study of non-covalent encapsulation methods for organic dyes into silica nanoparticles

Numerous luminophores may be encapsulated into silica nanoparticles (< 100 nm) using the reverse microemulsion process. Nevertheless, the behaviour and effect of such luminescent molecules appear to have been much less studied and may possibly prevent the encapsulation process from occurring. Such nanospheres represent attractive nanoplatforms for the development of biotargeted biocompatible luminescent tracers. Physical and chemical properties of the encapsulated molecules may be affected by the nanomatrix. This study examines the synthesis of different types of dispersed silica nanoparticles, the ability of the selected luminophores towards incorporation into the silica matrix of those nanoobjects as well as the photophysical properties of the produced dye-doped silica nanoparticles. The nanoparticles present mean diameters between 40 and 60 nm as shown by TEM analysis. Mainly, the photophysical characteristics of the dyes are retained upon their encapsulation into the silica matrix, leading to fluorescent silica nanoparticles. This feature article surveys recent research progress on the fabrication strategies of these dye-doped silica nanoparticles

Synthesis and dispersion of fluorescent nanoparticles dedicated to the fight against counterfeiting

Cette thèse aborde la thématique de la synthèse et de la dispersion de nanomatériaux luminescents (silice ou oxydes de terres rares) dédiés à la lutte anti-contrefaçon. La silice est synthétisée par un procédé sol-gel en microémulsion inverse. Des molécules fluorescentes organiques et organo-lanthanides sont incorporées dans les nanoparticules et il est montre que la nature du colorant influence son encapsulation. La fluorescence est obtenue sans lien covalent entre le colorant et la nanoparticule. Les nanoparticules sont ensuite fonctionnalisées dans le milieu de synthèse. Une nouvelle méthode de caractérisation de la fonctionnalisation est proposée et fait notamment apparaitre que la fonctionnalisation ainsi réalisée est homogène mais qu’a l’échelle de la nanoparticule, il y a apparition de nanodomaines. Les oxydes de terres rares sont obtenus par une collaboration. Deux traitements de surface sont particulièrement étudiés : une approche hybride consistant en l’encapsulation des nanoparticules dans une couche de polysiloxane suivie d’une fonctionnalisation adaptée ; et une approche basée sur l’adsorption d’agents tensioactifs. En particulier plusieurs agents tensioactifs représentatifs sont compares. Les nanoparticules ainsi traitées sont dispersées et stables en milieu liquide. Elles peuvent alors être incorporées dans différents polymères témoins (PMMA, PVA et PVC) et il est montre qu’une bonne dispersion en milieu liquide permet une incorporation homogène dans le polymère. Un essai industriel a été réalisé et a prouvé que certains de ces procédés développés pouvaient être transférés à l’échelle industrielleThis work deals with the synthesis and the dispersion of luminescent nanomaterials dedicated to the fight against counterfeiting. The nanomaterials (silica and rare earth oxides) own an optical code which is dispersed into the material to be tagged. The silica is synthesized by a reverse microemulsion sol-gel process. Organic fluorescent dyes and organo-lanthanides metal complexes are incorporated into the nanoparticles and it is shown that the nature of the dye influences its incorporation. The fluorescence is obtained without any covalent link between the dye and the silica matrix. After the synthesis, the nanoparticles are functionalized into the microemulsion. An original method is proposed to characterize the functionalization and it is shown that the functionalization is on the whole homogeneous but that at the nanoscale some nanodomains appear. The rare-earth oxides are obtained by collaboration. Two surface treatments are particularly studied : an hybrid approach based on the encapsulation of the nanoparticles into a polysiloxane shell followed by an adapted functionalization; and a second approach based on the use of surfactants. In particular, several well-known surfactants are compared. These modified nanoparticles are dispersed and stabilized into liquid media such as water or 2-Butanone. They are then incorporated into three polymers (PMMA, PVA and PVC) and it is shown that a good dispersion into a liquid allows obtaining an homogeneous incorporation into the polymers. An industrial test has been realized and has given the proof that some of these processes can be transferred directly at industrial scal

Z-contrast cryo-electron tomography probes shell porosity in multi-shell nanocomposites

International audienceStructures of nanoparticles are becoming increasingly complex as they keep acquiring multi-functionality. These nanoparticles often adopt a core–shell structure and comprise different types of materials. Their outer shell forms the interface between the particle core and the environment. and its porosity governs any material exchange. Current techniques for measuring porosity exist for microscopic samples but techniques adapted to nanoscale samples are wanting. We probed indirectly the porosity of an outer silica shell grown over silica nanospheres by means of metal-chelating agents located in the interior of the nanospheres. Using a high-tilt cryo-holder, we performed electron tomography with a high-angle annular dark field detector to determine the 3D structure of these multi-shell nanocomposites. Contamination was significantly reduced at 104 K. Tomographic reconstructions revealed the distribution of functional domains binding metal ions that had penetrated the porous silica shell around the core particle

Homogeneous dispersion of gadolinium oxide nanoparticles into a non-aqueous-based polymer by two surface treatments

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Lanthanide-chelate silica nanospheres as robust multicolor Vis-NIR tags.

International audienceDifferent lanthanide chelates have been simultaneously embedded in a silica matrix yielding bright dual-mode lanthanide doped nanospheres which are uniform in size distribution, tunable, photostable, and leakage free. Depending on the chelate combination, two color emission with a single light source or tunable emission with multiple sources is obtained

Lanthanide-chelate silica nanospheres as robust multicolor Vis-NIR tags

Different lanthanide chelates have been simultaneously embedded in a silica matrix yielding bright dual-mode lanthanide doped nanospheres which are uniform in size distribution, tunable, photostable, and leakage free. Depending on the chelate combination, two color emission with a single light source or tunable emission with multiple sources is obtained. © 2010 The Royal Society of Chemistry

Surface characterizations of fluorescent-functionalized silica nanoparticles: from the macroscale to the nanoscale

International audienceFluorescent silica nanoparticles are widely used for various applications from mechanical reinforcement to biology. In many cases, their surface has to be tailored. Herein fluorescent silica nanoparticles are synthesized by a reverse micro-emulsion process and functionalized by silane coupling agents owning amino and thiol groups. The functionalization is then characterized by macroscopic well-known methods (zeta potential, hydrophilic to hydrophobic ratio, etc.) and an original method based onto TEM observations of the contrast between the silica core and the metallic ions chelated by the functional groups grafted onto the surface is also introduced. This method reveals that the functionalization is effective and that it occurs by ''nano domains.'' It is therefore possible to characterize the functionalization by in situ observations. Finally, the characterized nanoparticles are incorporated into a PMMA thin film. The fluorescence of the nanoparticles allows the monitoring of the level of dispersion of the nanoparticles within the polymer and confirms all the other characterizations