Ratiometric Phosphorescent Silver Sensor: Detection and Quantification of Free Silver Ions within Silver Nanoparticles

Silver nanoparticles (AgNPs) have well-known antibacterial properties that have stimulated their widespread production and usage, which nonetheless concomitantly raises concerns regarding their release into the environment. Understanding the toxicity of AgNPs to biological systems, the environment, and the role that each silver species (Ag+ ions vs AgNPs) plays in that toxicity has received significant attention. One of the critical objectives of this research is the development of a reliable method that can sense and differentiate free silver ions from AgNPs and is able to characterize silver ions leaching from nanosilver. A number of analytical methods described in the literature that are available for sensing silver ions are costly, time consuming, tedious, and, more importantly, destroy the AgNP sample. To address these issues, a phosphorescent gold(I)-pyrazolate cyclic trinuclear complex (AuT) known to detect free silver ions was employed to detect and differentiate silver ions from AgNPs within an AgNP sample. The advantage of the proposed silver sensor is its ratiometric emission capability that undermines any background interference. The sensor exhibits a strong red emission (λmax = ∼690 nm) that, in the presence of Ag+ ions, will form a bright-green emissive adduct with a blue-shifted peak maximum near 475 nm yet red-shifted excitation peak. The presence of AgNPs did not inhibit the silver detection and quantification ability of the phosphorescent silver sensor. To understand the chemical transformation of nanosilver, the leaching of silver ions from AgNPs over a period of 35 days was monitored and quantified by measuring the I/Io changes of the sensor. Furthermore, through adduct formation, the AuT molecular system was able to remediate free silver ions from the solution. The stronger affinity of the AuT complex to “sandwich” free silver ions than AgNPs was demonstrated in the presence of KCl salt that is well documented to form AgCl in the presence of silver ions. To our knowledge, this is the only ratiometric luminescence-based silver sensor able to successfully differentiate between Ag+ ions and AgNPs, sense the silver leakage from AgNPs, and remediate toxic silver ions from an aqueous solution. The synthesis and characterization of this sensor is a simple, single-step process—anticipating its viability for various applications.