Reversible and selective luminescent determination of ClO⁻/H₂S redox cycle in vitro and in vivo based on a ruthenium trisbipyridyl probe

Abstract

A rapid and highly selective luminescent probe has been developed to determine the in vitro and in vivo ClO(-)/H2S redox cycle using a ruthenium tris-bipyridyl complex covalently linked with phenothiazine. The luminescence intensity was considerably enhanced upon the addition of ClO(-) due to the oxidation of the probe to its sulfoxide derivative, which quickly returned to the original level by the reaction with H2S due to the reconstitution of the probe. The redox cycle can be repeated at least 12 times. Under optimal conditions, the luminescence intensities are linear over the concentration range of 1 × 10(-9) to 1 × 10(-4) mol L(-1) for ClO(-) and 1 × 10(-9) to 1 × 10(-4) mol L(-1) for H2S, and the detection limits are 1.8 × 10(-11) mol L(-1) for ClO(-) and 1.2 × 10(-11) mol L(-1) for H2S, which are much lower than those obtained with other detection methods. The proposed method is simple in design and fast in operation, and is suitable for the reversible determination of ClO(-) and H2S in vitro and in vivo with high selectivity.

Reversible Fluorescent Probes for Biological Redox States

“…5 [36] GSH 488/5144 -fold decrease HeLa -H 2 O 2 , a-lipoic acid and NEM Chalcogenoxides Cy-PSe [37] ONOO À 758/7752 3.3-fold increase RAW264.7 -SIN-1, GST,L PS, IFN-g,P MA, NOC-5 and TEMPO MPh-Se-BOD [38] -OCl 460/475-650 5f old increase RAW264.7 -PMA, Taurine, Xanth./Xanth. oxidase HCSe [39] -OCl 510/5261 38-fold increase RAW264.7 -NaOCl and GSH NI-Se [40] -OCl 420/5231 2-fold increase RAW264.7 -LPS, PMA and SHA Mice -LPS diMPhSe-BOD [41] HOBr 610/635, 700 230-fold increase RAW264.7 -H 2 O 2 ,EPO, KBr and H 2 S Bis(BODIPY)diselenide [42] O 2 C À 504/5143 0-fold increase MCF-7/ADRc ells -P MA 2Me TeR [43] -OCl (COH), (ONOO -PTZ [45] HOCl 450/605 % 7-fold increase Mice -NaOCl, H 2 Sand PABA FO-PSe [46] HOCl 415 (800) TP / 520 % 40-fold increase RAW264.7 -PMA, ABAH Zebrafish -Z ymosan and Mice abdomen Flavins CMFL-BODIPY [47] n.a.…”

“…[37] Upon oxidation to Se=O, PET quenching is alleviated, thus resulting in aturn-on in fluorescence.Cy-PSe was reported to be selectively oxidized by peroxynitrite and [29,36,66] Figure 6. a) Reactivity of reversible chalcogenide/chalcogenoxide redox couple. Selected examples of this type of probe based on Se [37,42] (b) and either Te [44] or S [45] (c) are shown.…”

“…[45] Thes ulfur in the phenothiazine scaffold is selectively oxidized by hypochlorite (OCl À ), thus resulting in as ignificant luminescence increase.T his oxidation could be reversed in the presence of H 2 S. Ther eversible redox response could be repeated for at least 12 cycles,and [Ru(bpy) 3 …”

“…> 1000-fold increase 4T1 cells -2 ME, ascorbic acid, tiron, Mouse melanoma tumor tissue C.elegans -paraquat, tiron Chalcogenides RSe-N [34] GSH 525/530-640 % 6-fold increase HepG2, HL7702 -none Cy-O-Eb [35] H 2 O 2 768/794 % 8-fold increase HepG2 cells -GSH/H 2 O 2 redox cycles HepG2, HL7702 -BSO induced apoptosis Zebra fish larvae -tail fin wounding FSeSeF [36] GSH 488/5144 -fold decrease HeLa -H 2 O 2 , a-lipoic acid and NEM Chalcogenoxides Cy-PSe [37] ONOO À 758/7752 3.3-fold increase RAW264.7 -SIN-1, GST,L PS, IFN-g,P MA, NOC-5 and TEMPO MPh-Se-BOD [38] -OCl 460/475-650 5f old increase RAW264.7 -PMA, Taurine, Xanth./Xanth. oxidase HCSe [39] -OCl 510/5261 38-fold increase RAW264.7 -NaOCl and GSH NI-Se [40] -OCl 420/5231 2-fold increase RAW264.7 -LPS, PMA and SHA Mice -LPS diMPhSe-BOD [41] HOBr 610/635, 700 230-fold increase RAW264.7 -H 2 O 2 ,EPO, KBr and H 2 S Bis(BODIPY)diselenide [42] O 2 C À 504/5143 0-fold increase MCF-7/ADRc ells -P MA 2Me TeR [43] -OCl (COH), (ONOO À ) 600/6692 00-fold increase HL-60 cells -H 2 O 2 and ABAH Cy-NTe [44] ONOO À 793/820 % 80-fold increase RAW264.7 -LPS, IFN-g,PMA, AG, paraquat, NOC-5 and NaOCl BALB/c mice -L-cysteine, LPS, IFN-g,PMA, AG, GST [Ru(bpy) 3 ] 2+ -PTZ [45] HOCl 450/605 % 7-fold increase Mice -NaOCl, H 2 Sand PABA FO-PSe [46] HOCl 415 (800) TP / 520 % 40-fold increase RAW264.7 -PMA, ABAH Zebrafish -Z ymosan and Mice abdomen Flavins CMFL-BODIPY [47] n.a. 450/512 % 9-fold increase HeLa -Na 2 S 2 O 4 and H 2 O 2 NpFR1 [48] Global 405/5451 25-fold increase 3T3-L1 preadipocytes and differentiated adipoctyes -Glucose and H 2 O 2 NpFR2 [49] Global 488/5451 15-fold increase Mice bone marrow,thymus and spleen -H 2 O 2 and Mitotracker deep red.…”

Merocyanine Dye‐Based Fluorescent Chemosensor for Highly Selective and Sensitive Detection of Hypochlorous Acid and Imaging in Live Cells

“…[5] Excessive production of HClO leads to the several kidney diseases, Alzheimer's diseases, [6] atherosclerosis, amyotrophic lateral sclerosis, inflammatory and cancer. [7] Because of the biological importance of HClO, the development of highly selective and sensitive probes for hypochlorous acid has become an important issue. [8][9][10] The fluorescent fluorophores have been very important tools to detect biological system in recent years, due to their high sensitivity and selectivity and real time detection.…”