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Abstract
A new fluorescent chemosensor 1, which based on hydroxyapatite (HA) nanoparticles covalently functionalized with a difluoroboron dipyrromethene, has been prepared by nucleophilic substitution of the fluorescent dye 3-chloro-4,4-difluoro-8-(4-tolyl)-5-[bis(pyridine2-ylmethyl)amino]-4-bora-3a,4a-diaza-s-indacene (2) with surface-modified HA nanoparticles. The HA particles were prepared by using SiO2 as templates (THA) with 3-(aminopropyl)triethoxysilane (THA-APTES). Substitution of the electron-withdrawing chlorine in 2 by an electron-donating amino group of HA changes the properties of the nanoparticles 1 and the corresponding fluorescent dye 2. Absorption and emission maxima of 1 in ethanol are red-shifted by 75 and 30 nm, respectively, in comparison with those of 2. In contrast to no selectivity of dye 2 for Cd2+ or Zn2+ in EtOH/H2O (95/5 V/V) solutions, the nanofluorescent probe 1 forms 1 : 1 complexes with Cd2+ or Zn2+, producing an instant color change along with large hypsochromic shifts in the absorption and fluorescence spectra by 70 and 35 nm, respectively, and large cation-induced fluorescence amplifications.
Acknowledgment
This work was supported by the Chinese “Program for New Century Excellent Talents in University” (NCET-09-0444), the ”Fundamental Research Funds for the Central Universities” (lzujbky-2011-22 and lzujbky-2012-k13), the National Science Foundation for Fostering Talents in Basic Research of the National Natural Science Foundation of China (Grant No. J1103307) and the “International Cooperation Program of Gansu Province” (1104WCGA182). The authors would like to thank the Natural Science Foundation of China (No. 21271094), and this study was supported in part by the “Key Program of National Natural Science Foundation of China” (20931003).