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Reduced texaphyrin: A ratiometric optical sensor for heavy metals in aqueous solution

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We report here a water-soluble metal cation sensor system based on the as-prepared or reduced form of an expanded porphyrin, texaphyrin. Upon metal complexation, a change in the redox state of the ligand occurs that is accompanied by a color change from red to green. Although long employed for synthesis in organic media, we have now found that this complexation-driven redox behavior may be used to achieve the naked eye detectable colorimetric sensing of several number of less-common metal ions in aqueous media. Exposure to In(III), Hg(II), Cd(II), Mn(II), Bi(III), Co(II), and Pb(II) cations leads to a colorimetric response within 10 min. This process is selective for Hg(II) under conditions of competitive analysis. Furthermore, among the subset of response-producing cations, In(III) proved unique in giving rise to a ratiometric change in the ligand-based fluorescence features, including an overall increase in intensity. The cation selectivity observed in aqueous media stands in contrast to what is seen in organic solvents, where a wide range of texaphyrin metal complexes may be prepared. The formation of metal cation complexes under the present aqueous conditions was confirmed by reversed phase high-performance liquid chromatography, ultra-violet-visible absorption and fluorescence spectroscopies, and high-resolution mass spectrometry.

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This work was supported by the National Institutes of Health (Grants CA68682 to J.L.S.) and the Robert A. Welch Foundation (F-0018). HDR would like to thank UT Austin for a Scientist in Residence Fellowship and the Los Alamos National Lab for a Seaborg Fellowship.

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Correspondence to Jonathan L. Sessler.

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Root, H.D., Thiabaud, G. & Sessler, J.L. Reduced texaphyrin: A ratiometric optical sensor for heavy metals in aqueous solution. Front. Chem. Sci. Eng. 14, 19–27 (2020). https://doi.org/10.1007/s11705-019-1888-y

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  • texaphyrin
  • fluorescent sensor
  • ion-sensing
  • indium
  • mercury