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

doi:10.1007/s11705-019-1888-y

Front. Chem. Sci. Eng.

2020, Vol. 14

Issue (1) : 19-27 https://doi.org/10.1007/s11705-019-1888-y

RESEARCH ARTICLE

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

Harrison D. Root, Gregory Thiabaud, Jonathan L. Sessler(

)

Department of Chemistry, The University of Texas at Austin, Austin, TX 78712-1224, USA

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Abstract

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.

Keywords texaphyrin fluorescent sensor ion-sensing indium mercury

Corresponding Author(s): Jonathan L. Sessler

Online First Date: 07 January 2020 Issue Date: 20 January 2020

Cite this article:

Harrison D. Root,Gregory Thiabaud,Jonathan L. Sessler. Reduced texaphyrin: A ratiometric optical sensor for heavy metals in aqueous solution[J]. Front. Chem. Sci. Eng., 2020, 14(1): 19-27.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1888-y
https://academic.hep.com.cn/fcse/EN/Y2020/V14/I1/19

Fig.1 The reduced form of texaphyrin, referred to as sp3-Tex (1), is red. It turns green upon metalation and concomitant oxidation. This color change results from the aromatization of the initial ligand (left) to produce the corresponding metal complex 2 (right).

Fig.2 Scheme 1 Synthetic procedure used to obtain sp3-Tex (1).

Fig.3 Photographs of solutions obtained when the indicated metal salts (10 equiv. from a 100 mmol?L^?¹ solution in an acetic acid: NH₄OAc= 1 : 1 aqueous buffer) are mixed with sp3-Tex (0.1 mmol?L^?¹ in 0.1 mol?L^?¹ NH₄OAc buffer) and heated at 90ºC for 10 min (pH ≈ 5?6). Cations that were found to provide a response were Mn(OAc)₂, Co(NO₃)₃, CoCl₃, Cd(NO₃)₃, InCl₃, Hg(OAc)₂, Pb(NO₃)₂, and Bi(OAc)₃. The acetic acid : NH₄OAc= 1 : 1 aqueous buffer was used to convert all cations to their respective acetate derivatives and to control for putative anion effects.

Fig.4 Fluorescence spectra at different concentrations of a solution of sp3-Tex (0.1 mmol?L^?¹ in aqueous acetate buffer) and InCl₃ (1 mmol?L^?¹ in aqueous acetate buffer), then diluted to the indicated concentrations (l_max = 752 nm, left) and fluorescence of pre-formed In(III)-texaphyrin complex (In(III)-Tex) in methanol (l_max = 748 nm, right).

Fig.5 (a) Fluorescence spectra of sp3-Tex recorded in the presence of increasing concentrations of In(III); (b) Change in fluorescence intensity at 525 nm and 752 nm seen in the presence of increasing concentrations of In(III); (c) Ratio of fluorescence signal at 752 nm and 525 nm as a function of increasing In(III) concentration.

Fig.6 The fluorescence emitted by In(III)-texaphyrin can be observed by the naked eye down to a concentration of roughly 10 µmol?L^?¹in methanol when solutions containing low concentrations of sp3-Tex and an In(III) source are subject to illumination using a simple handheld UV lamp.

Fig.7 (a) Reaction scheme, (b) HPLC trace l_detector = 470 nm, (c) high-resolution mass spectrum (d) fluorescence change l_ex = 470 nm, and (e) UV-Vis absorption for solutions prepared by mixing InCl₃ with sp3-Tex (1) under the indicated experimental conditions.

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