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

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.

Key words： texaphyrin; fluorescent sensor; ion-sensing; indium; mercury

Acknowledgements

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.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-019-1888-y and is accessible for authorized users.

References

1 Wu D, Sedgwick A C, Gunnlaugsson T, Akkaya E U, Yoon J, James T D. Fluorescent chemosensors: The past, present, and future. Chemical Society Review , 2017, 46(23): 7105–7123

2 Li Z, Askim J R, Suslick K S. The optoelectronic nose: Colorimetric and fluorometric sensor arrays. Chemical Reviews, 2019, 119(1): 231–292

3 Kaur B, Kaur N, Kumar S. Colorimetric metal ion sensors—a comprehensive review of the years 2011‒2016. Coordination Chemistry Reviews, 2018, 358: 13–69

4 Piriya A, Joseph P, Daniel K, Lakshmanan S, Kinoshita T, Muthusamy S. Colorimetric sensors for rapid detection of various analytes. Materials Science and Engineering C, 2017, 78: 1231–1245

5 Long F, Zhu A, Shi H, Wang H, Liu J. Rapid on-site/in-situ detection of heavy metal ions in environmental water using a structure-switching DNA optical biosensor. Scientific Reports, 2013, 3(1): 1–7

6 Zhou W, Saran R, Liu J. Metal sensing by DNA. Chemical Reviews, 2017, 117(12): 8272–8325

7 Nolan E M, Lippard S J. Turn-on and ratiometric mercury sensing in water with a red-emitting probe. Journal of the American Chemical Society, 2007, 129(18): 5910–5918

8 Azmi N A, Ahmad S H, Low S C. Detection of mercury ions in water using a membrane-based colorimetric sensor. RSC Advances, 2018, 8(1): 251–261

9 Chang J, Zhou G, Gao X, Mao S, Cui S, Ocola L E, Yuan C, Chen J. Real-time detection of mercury ions in water using a reduced graphene oxide/DNA field-effect transistor with assistance of a passivation layer. Sensing and Bio-Sensing Research, 2015, 5: 97–104

10 Karthikeyan K, Sujatha L. Fluorometric sensor for mercury ion detection in a fluidic MEMS device. IEEE Sensors Journal, 2018, 18(13): 5225–5231

11 Maher S, Bastani B, Smith B, Jjunju Z, Taylor S, Young I S. Portable fluorescent sensing array for monitoring heavy metals in water. IEEE Sensors, 2016: 1–3

12 He W, Luo L, Liu Q, Chen Z. Colorimetric sensor array for discrimination of heavy metal ions in aqueous solution based on three kinds of thiols as receptors. Analytical Chemistry, 2018, 90(7): 4770–4775

13 Niu L, Li H, Feng L, Guan Y, Chen Y, Duan C, Wu L, Guan Y, Tung C, Yang Q. BODIPY-based fluorometric sensor array for the highly sensitive identification of heavy-metal ions. Analytica Chimica Acta, 2013, 775: 93–99

14 Singh R K, Mishra S, Jena S, Panigrahi B, Das B, Jayabalan R, Parhi P K, Mandal D. Rapid colorimetric sensing of gadolinium by EGCG-derived AgNPs: The development of a nanohybrid bioimaging probe. Chemical Communications, 2018, 54(32): 3981–3984

15 Denis M, Pancholi J, Jobe K, Watkinson M, Goldup S M. Chelating rotaxane ligands as fluorescent sensors for metal ions. Angewandte Chemie International Edition, 2018, 57(19): 5310–5314

16 Hong W, Li W, Hu X, Zhao B, Zhang F, Zhang D. Highly sensitive colorimetric sensing for heavy metal ions by strong polyelectrolyte photonic hydrogels. Journal of Materials Chemistry, 2011, 21(43): 17193–17201

17 Moghaddam M R, Carrara S, Hogan C F. Multi-colour bipolar electrochemiluminescence for heavy metal ion detection. Chemical Communications, 2018, 55(8): 3–6

18 Boening D W. Ecological effects, transport, and fate of Mercury: A general review. Chemosphere, 2000, 40(12): 1335–1351

19 Zheng W, Aschner M, Ghersi-egea J. Brain barrier systems: A new frontier in metal neurotoxicological research. Toxicology and Applied Pharmacology, 2003, 192(1): 1–11

20 Selid P D, Xu H, Collins E M, Face-Collins M S, Zhao J X. Sensing mercury for biomedical and environmental monitoring. Sensors (Basel), 2009, 9(7): 5446–5459

21 Hu J, Wu T, Zhang G, Liu S. Highly selective fluorescence sensing of mercury ions over a broad concentration range based on mixed polymeric micelles. Macromolecules, 2012, 45(9): 3939–3947

22 Nolan E M, Lippard S J. Tools and tactics for the optical detection of mercuric ion. Chemical Reviews, 2008, 108(9): 3443–3480

23 Zhang K, Wu Y, Wang W, Li B, Zhang Y, Zuo T. Resources, conservation and recycling indium from waste LCDs: A review. Resources, Conservation and Recycling, 2015, 104: 276–290

24 Thakur M L, Welch M J, Joist J H, Coleman R E. Indium-III labeled platelets: Studies on preparation and evaluation of in vitro and in vivo functions. Thrombosis Research, 1976, 9(4): 345–357

25 Thakur M, Lavender J P, Arnot R, Silvester D J, Segal A W. Indium-III-labeled autologous leukocytes in man. Journal of Nuclear Medicine, 1977, 18(10): 1014–1021

26 Zolata H, Abbasi F, Afarideh H. Synthesis, characterization and theranostic evaluation of indium-III labeled multifunctional superparamagnetic iron oxide nanoparticles. Nuclear Medicine and Biology, 2015, 42(2): 164–170

27 Alfantazi A M, Moskalyk R R. Processing of indium: A review. Materials & Design, 2003, 16(8): 687–694

28 Lim C H, Han J, Cho H, Kang M. Studies on the toxicity and distribution of indium compounds according to particle size in sprague-dawley rats. Toxicological Research, 2014, 30(1): 55–63

29 Tanaka A, Hirata M, Kiyohara Y, Nakano M, Omae K, Shiratani M, Koga K. Review of pulmonary toxicity of indium compounds to animals and humans. Thin Solid Films, 2010, 518(11): 2934–2936

30 Mehta P K, Hwang G W, Park J, Lee K. Highly sensitive ratiometric fluorescent detection of indium(III) using fluorescent probe based on phosphoserine as a receptor. Analytical Chemistry, 2018, 90(19): 11256–11264

31 Wu Y C, Li H, Yang H. A sensitive and highly selective fluorescent sensor for In³⁺. Organic & Biomolecular Chemistry, 2010, 8(15): 3394–3397

32 Kim S K, Kim S H, Kim H J, Lee S H, Lee S W, Ko J, Bartsch R A, Kim J S. Indium (III)-induced fluorescent excimer formation and extinction in calix[4]arene—fluoroionophores. Inorganic Chemistry, 2005, 44(22): 7866–7875

33 Ding Y, Zhu W, Xie Y. Development of ion chemosensors based on porphyrin analogues. Chemical Reviews, 2017, 117(4): 2203–2256

34 Sessler J L, Mody T D, Hemmi G W, Lynch V. Synthesis and structural characterization of lanthanide(III) texaphyrins. Inorganic Chemistry, 1993, 32(14): 3175–3187

35 Preihs C, Arambula J F, Lynch V M, Siddik H, Sessler J L. Bismuth- and lead-texaphyrin complexes: Towards potential α-core emitters for radiotherapy. Chemical Communications, 2010, 46(42): 7900–7902

36 Thiabaud G, Radchenko V, Wilson J J, John K D, Birnbaum E R, Sessler J L. Rapid insertion of bismuth radioactive isotopes into texaphyrin in aqueous media. Journal of Porphyrins and Phthalocyanines, 2017, 21(12): 882–886

37 Maiya B G, Harriman A, Sessler J L, Hemmi G, Murai T, Mallouk T E. Ground- and excited-state spectral and redox properties of cadmium(II) texaphyrin. Journal of Physical Chemistry, 1989, 93(24): 8111–8115

38 Sessler J L, Murai T, Lynch V, Cyr M. An “expanded porphyrin”: The synthesis and structure of a new aromatic pentadentate ligand of chemistry. Journal of the American Chemical Society, 1988, 110(16): 5586–5588

39 Sessler J L, Dow W C, Connor D O, Harriman A, Hemmi G, Mody T D, Miller R A, Qing F, Springs S, Woodburn K, Biomedical applications of lanthanide(III) texaphyrins lutetium(III) texaphyrins as potential photodynamic therapy photosensitizers. Journal of Alloys and Compounds, 1997, 249(1-2): 146–152

40 Magda D, Miller R A. Motexafin gadolinium: A novel redox active drug for cancer therapy. Seminars in Cancer Biology, 2006, 16(6): 466–476

41 Hannah S, Lynch V, Guldi D M, Gerasimchuk N, Macdonald C L B, Magda D, Sessler J L. Late first-row transition-metal complexes of texaphyrin. Journal of the American Chemical Society, 2002, 124(28): 8416–8427

42 Thiabaud G, Arambula J F, Siddik Z H, Sessler J L. Photoinduced reduction of Pt IV within an anti-proliferative Pt IV-texaphyrin conjugate. Chemistry (Weinheim an der Bergstrasse, Germany), 2014, 20(29): 8942–8947

43 Thiabaud G, Mccall R, He G, Arambula J F, Siddik Z H, Sessler J L. Activation of platinum(IV) prodrugs by motexafin gadolinium as a redox mediator. Angewandte Chemie International Edition, 2016, 55(41): 12626–12631

44 Arambula J F, Sessler J L, Siddik Z H. Overcoming biochemical pharmacologic mechanisms of platinum resistance with a texaphyrin-platinum conjugate. Bioorganic & Medicinal Chemistry Letters, 2011, 21(6): 1701–1705

45 Arambula J F, Sessler J L, Siddik Z H. A texaphyrin-oxaliplatin conjugate that overcomes both pharmacologic and molecular mechanisms of cisplatin resistance in cancer cells. MedChemComm, 2012, 3(10): 1275–1281

46 Lee M H, Kim E J, Park S Y, Hong K S, Kim S, Sessler J L. Acid-triggered release of doxorubicin from a hydrazone-linked Gd³⁺-texaphyrin conjugate. Chemical Communications, 2016, 52(69): 10551–10554

47 Blesic M, Melo E, Petrovski Z, Plechkova N V, Lopes N C, Seddon K R, Rebelo P N. On the self-aggregation and fluorescence quenching aptitude of surfactant ionic liquids. Journal of Physical Chemistry B, 2008, 112(29): 8645–8650

48 Mei J, Leung N L C, Kwok R T K, Lam J W Y, Tang B Z. Aggregation-induced emission: Together we shine, united we soar! Chemical Reviews, 2015, 115(21): 11718–11940

49 Quinn S D, Magennis S W. Optical detection of gadolinium(III) ions via quantum dot aggregation. RSC Advances, 2017, 7(40): 24730–24735