Aggregation-Switching Strategy for Promoting Fluorescent Sensing of Biologically Relevant Species: A Simple Near-Infrared Cyanine Dye Highly Sensitive and Selective for ATP

• Published in: Analytical chemistry (Washington) 2017-06, Vol.89 (11), p.6210-6215
• Main Authors: Zhang, Peng, Zhu, Meng-Si, Luo, Hao, Zhang, Qian, Guo, Lin-E, Li, Zhao, Jiang, Yun-Bao
• Format: Article
• Language: English
• Subjects: Agglomeration; Aggregates; Amplification; Aqueous solutions; ATP; Bearing; Binding sites; Chemistry; Detection; Dispersion; Dodecyltrimethylammonium bromide; Dyes; Electrostatic properties; Emission; Fluorescence; Fluorescent dyes; Fluorescent indicators; I.R. radiation; Molecules; Near infrared radiation; Quenching; Receptors; Selectivity; Strategy; Switches; Switching; Vesicles
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/acs.analchem.7b01175

We report a strategy for enhanced performance of fluorescent sensing of biologically relevant species that often bind with natural receptors via multiple interactions. We propose making a fluorescent sensory molecule to form H-aggregates such that its emission is quenched leaving a low background, and upon binding to a biologically relevant species, the aggregate switches to another form in which the fluorescent species is better protected to afford a stronger emission signal. Meanwhile, the aggregated fluorescent dyes afford multiple interactions with the sensing species that require multiple binding sites. The lower background, stronger binding, and stronger signal would therefore lead to a much higher sensing performance, as improved selectivity would also result in along with the signal amplification. We thus designed a near-IR cyanine dye bearing two boronic acid groups (Cy-BA) for fluorescent sensing of ATP such that the boronic acid groups in the dye molecule bind to the cis-diol moiety in ATP. Introduction of the cationic surfactant dodecyltrimethylammonium bromide (DTAB) below its critical aggregation concentration is key because Cy-BA molecules made into H-aggregates were practically nonfluorescent. Upon mixing with ATP, a dramatic enhancement in the fluorescence occurred because of the formation of ATP/Cy-BA/DTAB vesicles in which the fluorescent dye is well dispersed and protected. This sensing scheme, despite the dynamic nature of the boronic acid/cis-diol interaction, weakness of the electrostatic interactions among ATP/Cy-BA/DTAB, and poor selectivity of these interactions, allows for highly sensitive and selective detection of ATP in aqueous solution.