Upconversion Luminescent Chemodosimeter Based on NIR Organic Dye for Monitoring Methylmercury In Vivo

While most luminescent organic dyes display intense Stokes fluorescence, some of them exhibit unique single‐photon frequency upconversion luminescence (FUCL). Compared to conventional anti‐Stokes luminescence of lanthanides and two‐photon excitation, FUCL materials display adjustable spectrum area and require a much lower excitation power. Although this is very beneficial for biological applications in the perspective of reducing photodamage to biological samples and photobleaching of the dyes, the utilization of FUCL for biosensing and bioimaging in vivo has not been reported. In this study, we developed a near‐infrared (NIR) rhodamine derivative (FUC‐1) as a chemodosimeter, which displays weak luminescence but undergoes thiolactone ring‐open process leading to luminescence turn‐on in response to mercury(II) cation or methylmercury with good selectivity and high sensitivity in aqueous solution. Interestingly, FUC‐1 displays particular FUCL, excitation at 808 nm leads to luminescence at 745 nm. Compared to Stokes luminescence resulted from excitation at 630 nm, the use of FUCL lowers the detection limit of Hg²⁺ to be 0.207 nM. FUC‐1 has been used for FUCL bioimaging of methylmercury in live cells and mice. To the best of our knowledge, this is the first example of FUCL biosensing and bioimaging in vivo using visible and NIR fluorescence of small‐molecular dyes.