Ganguly Mainak, Pal Jaya, Mondal Chanchal, Pal Anjali, Pal Tarasankar
Department of Chemistry, Furman University, Greenville, South Carolina-29613, USA.
Dalton Trans. 2015 Mar 7;44(9):4370-9. doi: 10.1039/c4dt04022h.
Metal enhanced fluorescence (MEF) from organic molecules has been the focus of plasmonic/photonic research. In this regard, silver and gold particle stimulated fluorescence has received much attention. However, the involvement of small organic molecules in solution has not been accounted for in MEF. We have reported here that the aqueous alkaline solution of salicylaldehyde exhibits highly enhanced fluorescence at room temperature (λ(em) ∼ 420 nm, Stokes shift 120 nm, stability > a year) in the presence of Ag(I) or Au(III) after simple ageing for two days. The increased scattering cross-section of the in situ produced aggregated metal particles and the lightening rod effect of the metal aggregates that concentrate the electric field around the fluorophore (i.e., alkaline solutions of salicylaldehyde) are ascribed to such extraordinary fluorescence enhancement caused by Ag and Au particles. Finally, selective fluorescence enhancement due to silver particles alone has been made possible in the presence of ammonia or primary amines due to imine bond formation that eliminates Au enhanced fluorescence quantitatively. This finding allows us to design a highly selective Ag(I) sensor in the solution phase with a cheap and commercially available compound with LOD far below EPA-permissible levels. The imine induced selective silver enhanced fluorescence phenomenon becomes a general matter in our studies even with different Schiff bases.
有机分子的金属增强荧光(MEF)一直是等离子体/光子学研究的重点。在这方面,银和金颗粒激发的荧光受到了广泛关注。然而,MEF尚未考虑溶液中有机小分子的参与情况。我们在此报告,水杨醛的碱性水溶液在室温下(发射波长λ(em) ∼ 420 nm,斯托克斯位移120 nm,稳定性>一年),在简单老化两天后,在Ag(I)或Au(III)存在的情况下表现出高度增强的荧光。原位生成的聚集金属颗粒散射截面的增加以及金属聚集体在荧光团(即水杨醛碱性溶液)周围集中电场的避雷针效应,被认为是由银和金颗粒引起的这种非凡荧光增强的原因。最后,由于氨或伯胺存在时形成亚胺键,定量消除了金增强的荧光,使得仅由银颗粒引起的选择性荧光增强成为可能。这一发现使我们能够用一种廉价且市售的化合物设计出一种溶液相高选择性Ag(I)传感器,其检测限远低于美国环保署允许的水平。即使使用不同的席夫碱,亚胺诱导的选择性银增强荧光现象在我们的研究中也成为一种普遍现象。