Silica-Coated CaF₂:Eu3+ Nanoparticles Functionalized with Oxalic Acid for Bio-conjugation to BSA Proteins

摘要

A new method for silica-coated CaF₂:Eu3+ core-shell nanoparticles functionalized with oxalic acid for bio-conjugation to bovine serum albumin (BSA) proteins has been developed. Moreover, CaF₂:Eu3+/SiO₂ core-shell nanoparticles modified with oxalic acid are biocompatible and can be dispersed in water. As an organic functional molecule, oxalic acid is able to react with hydroxyl groups existed on the surface of SiO₂ layer by esterification reaction to form carboxylic acid for further bio-conjugation with BSA. The final products were characterized by means of X-ray diffraction (XRD), transmission electron microscope (TEM), field-emission scanning electron microscopy (FE-SEM), ultraviolet (UV) spectrophotometer, infrared (IR) spectrophotometer and photoluminescence (PL) spectra. XRD result confirmed the phase purity of CaF₂:10 mol% Eu3+ and CaF₂:10 mol% Eu3+/SiO₂ nanoparticles obtained from the quaternary reverse micelles of cetyltrimethylammonium bromide (CTAB), cyclohexane, n-pentanol and water. Images of TEM and FE-SEM showed that the average grain sizes of CaF₂:10 mol% Eu3+/SiO₂ and bio-conjugation of CaF₂:10 mol% Eu3+/SiO₂ nanoparticles with BSA were about 17 nm. The patterns of UV and IR spectra showed that BSA was linked to CaF₂:10 mol% Eu3+/SiO₂ nanoparticles. In the emission spectrum of CaF₂:10 mol% Eu3+/SiO₂ conjugated by BSA nanoparticles, characteristic emission peaks of Eu3+ within the wavelength ranging from 500 to 700 nm were observed, which is corresponding to the transitions from the excited 5D₀ levels to 7F_J levels. This confirmed that the Eu3+ dopant ion is located in a Ca2+ crystal site with T_dsymmetry. CaF₂:10 mol% Eu3+/SiO₂ conjugated by BSA nanoparticles remain stable in aqueous media within 15 d with pH ranging from 2 to 9. Therefore, these luminescent colloidal nanoparticles can be potentially employed as targeted fluorescent labels in biomedical research applications.