RESUMEN
The present work introduces deliberate synthesis of Gd(III)-doped silica nanoparticles with high relaxivity at magnetic field strengths below 1.5T. Modified microemulsion water-in-oil procedure was used in order to achieve superficial localization of Gd(III) complexes within 40-55nm sized silica spheres. The relaxivities of the prepared nanoparticles were measured at 0.47, 1.41 and 1.5T with the use of both NMR analyzer and whole body NMR scanner. Longitudinal relaxivities of the obtained silica nanoparticles reveal significant dependence on the confinement mode, changing from 4.1 to 49.6mM-1s-1 at 0.47T when the localization of Gd(III) complexes changes from core to superficial zones of the silica spheres. The results highlight predominant contribution of the complexes located close to silica/water interface to the relaxivity of the nanoparticles. Low effect of blood proteins on the relaxivity in the aqueous colloids of the nanoparticles was exemplified by serum bovine albumin. T1- weighted MRI data indicate that the nanoparticles provide strong positive contrast at 1.5T, which along with low cytotoxicity effect make a good basis for their application as contrast agents.
Asunto(s)
Calixarenos/química , Medios de Contraste/síntesis química , Gadolinio/química , Imagen por Resonancia Magnética/métodos , Dióxido de Silicio/química , Animales , Bovinos , Supervivencia Celular/efectos de los fármacos , Medios de Contraste/farmacología , Gadolinio/farmacología , Humanos , Linfocitos/citología , Linfocitos/efectos de los fármacos , Espectroscopía de Resonancia Magnética , Nanopartículas/química , Cultivo Primario de Células , Albúmina Sérica Bovina/química , Silanos/químicaRESUMEN
The quenching effect of dyes (phenol red and bromothymol blue) on Tb(III)-centered luminescence enables to sense the aggregation of cationic and anionic surfactants near the silica surface of Tb-doped silica nanoparticles (SN) in aqueous solutions. The Tb-centered luminescence of non-decorated SNs is diminished by the inner filter effect of both dyes. The decoration of the silica surface by cationic surfactants induces the quenching through the energy transfer between silica coated Tb(III) complexes and dye anions inserted into surfactant aggregates. Thus the distribution of surfactants aggregates at the silica/water interface and in the bulk of solution greatly affects dynamic quenching efficiency. The displacement of dye anions from the interfacial surfactant adlayer by anionic surfactants and phospholipids is accompanied by the "off-on" switching of Tb(III)-centered luminescence.
Asunto(s)
Nanopartículas/química , Fosfolípidos/química , Dióxido de Silicio/química , Tensoactivos/química , Terbio/química , Absorción , Azul de Bromotimol/química , Cationes , Cetrimonio , Compuestos de Cetrimonio/química , Fluorescencia , Hidrodinámica , Fenolsulfonftaleína/química , Fosfatidilgliceroles/química , Dodecil Sulfato de Sodio/química , Análisis Espectral , Electricidad EstáticaRESUMEN
Novel silica-coated Tb(III) nanoparticles with high luminecsence were synthesized using the reverse microemulsion procedure. The quenching of luminescent properties of these nanoparticles can be achieved by ion exchange and energy transfer mechanisms. The quenching through the ion exchange of Tb(III) by H+ or La(III) is time dependent, indicating that the ion exchange is probably diffusion controlled. The quenching by Co(III) complex cations is achieved by the energy transfer mechanism and thus is not time dependent. The analysis of quenching data in Stern-Volmer cooordinates reveal the negative charge of the silica-coated Tb(III)-TCAS nanoparticles and several types of luminophoric species, located within the core and close to the surface of silica nanoparticles.