Interaction of LiYF4:Yb3+/Er3+/Ho3+/Tm3+@LiYF4:Yb3+ upconversion nanoparticles, molecularly imprinted polymers, and templates

Abstract

In this work, LiYF₄:Yb_0.25³⁺/Er_0.01³⁺/Tm_0.01³⁺/Ho_0.01³⁺@LiYF₄:Yb_0.2³⁺ upconverting nanoparticles (UCNP) were used as luminescent materials for the preparation of molecular imprinting polymer nanocomposites. Three luminescent molecularly imprinted polymer (MIP) nanocomposites were prepared by in situ polymerization. The relationship between the functional monomers, templates, and upconversion nanoparticles was investigated. Two hydrophilic monomers (acrylic acid (AA) and acrylamide (AAm)) and one hydrophobic monomer (N-tert-butylacrylamide (TBAm)) were employed as functional monomers, while one amino acid (cysteine) and two proteins (albumin and hemoglobin) were employed as the templates to investigate the effect of their interaction with LiYF₄:Yb³⁺/Er³⁺/Ho³⁺/Tm³⁺@LiYF₄:Yb³⁺ core/shell UCNPs on the polymerization process, luminescence properties, and adsorption capacity. The results showed that the UCNPs were embedded in the polymeric matrix to form an irregular quasimicrospherical UCNPs@MIP with diameters ranging from several hundred nanometers to several micrometers depending on the functional monomer. The quenching effect was more pronounced for the adsorption of hemoglobin with UCNPs@MIP compared to cysteine and albumin. In addition, the adsorption capacities of the AA- and AAm-made UCNPs@MIP were greater than those of TBAm-made UCNPs@MIP. The rebinding of the templates onto UCNPs@MIP was very fast and approached equilibrium within 30 min, indicating that the synthesized UCNPs@MIP can be employed as fluorescent probes to offer rapid detection of molecules.