Enhancing the fluorescence of organic dye by colloidal particles is one of the most promising routes to optimize fluorescence detection. However, in addition to metallic particles, which serve as the most frequently used particles and have been found to employ the plasmonic resonance to provide strong fluorescence enhancement, neither new types of colloidal particles nor new fluorescence mechanisms have been intensively explored in recent years. In this work, strongly enhanced fluorescence was observed when 2-(2-hydroxyphenyl)-1H-benzimidazole (HPBI) molecules were simply mixed with zeolitic imidazolate framework-8 (ZIF-8) colloidal suspensions. Moreover, the enhancement factor ΔI = IHPBI+ZIF-8/IHPBI does not increase accordingly with the increasing amount of HPBI. To find out how the strong fluorescence was triggered and affected by the amount of HPBI, multiple techniques were applied to analyze the adsorption behavior. By combining analytical ultracentrifugation with first-principles calculations, we proposed that HPBI molecules were adsorbed onto the surface of ZIF-8 particles coordinatively and electrostatically, depending on the concentration of HPBI molecules. The coordinative adsorption would result in a new kind of fluorescence emitter. The new fluorescence emitters tend to distribute on the outer surface of ZIF-8 particles periodically. The distance between each fluorescence emitter is fixed and much smaller than the wavelength of the excitation light. Thus, it can be concluded that collective spontaneous emission might be triggered.
Yuyi Zhang,Wei Zhang,Yajie Bian,Yiting Liu,Xiaolei Zhang,Mengdi Chen,Bingwen Hu,Qingyuan Jin
Zeolitic imidazolate framework-8 (ZIF-8) is one of the most promising metal–organic frameworks because of its excellent high porosity, stability and geometrically well-defined structure. However, the application of ZIF-8 in the field of fluorescent molecular sensing has not been intensively explored. Our work demonstrates the versatility of ZIF-8 as a carrier material, which can be used for small molecule [2-(2-hydroxyphenyl)-1H-benzimidazole (HPBI)] capture and fluorescence enhancement. ZIF-8 displays luminescent behavior changes when combined with HPBI, as the emission peaks of ZIF-8 and HPBI are located in the same range for resonance enhancement of fluorescence. The results of the experiment indicate that the fluorescence enhancement effect will change in the presence of different concentrations of HPBI. We propose that the pore structure of ZIF-8 could provide an opportunity for the adsorption of HPBI molecules, and eventually the adsorption would saturate. The high porosity of ZIF-8 provides the path to HPBI aggregation or entrance into the ZIF-8 internal structure. Our results suggest that ZIF-8 may offer great promise for molecular fluorescence sensing.