Tracking isotopically labeled oxidants using boronate-based redox probes

Ríos, Natalia; Radí, Rafael; Kalyanaraman, Balaraman; Zielonka, Jacek

doi:10.1074/jbc.ra120.013402

Cited by 18 publications

(19 citation statements)

References 86 publications

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“…7 , Supplementary Figure S5 and Table S4 ). To our knowledge, this is the first direct observation of this reaction, and it explains the recently reported incorporation of an oxygen atom from in the product 56 .…”

Section: Discussionsupporting

confidence: 72%

Oxidation of ethidium-based probes by biological radicals: mechanism, kinetics and implications for the detection of superoxide

Michalski

Thiebaut

Ayhan

et al. 2020

Sci Rep

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Hydroethidine (HE) and hydropropidine ($$\hbox {HPr}^{+}$$ HPr + ) are fluorogenic probes used for the detection of the intra- and extracellular superoxide radical anion ($$\hbox {O}_{ {2}}^{\bullet -}$$ O 2 ∙ - ). In this study, we provide evidence that HE and $$\hbox {HPr}^{+}$$ HPr + react rapidly with the biologically relevant radicals, including the hydroxyl radical, peroxyl radicals, the trioxidocarbonate radical anion, nitrogen dioxide, and the glutathionyl radical, via one-electron oxidation, forming the corresponding radical cations. At physiological pH, the radical cations of the probes react rapidly with $$\hbox {O}_{ {2}}^{\bullet -}$$ O 2 ∙ - , leading to the specific 2-hydroxylated cationic products. We determined the rate constants of the reaction between $$\hbox {O}_{ {2}}^{\bullet -}$$ O 2 ∙ - and the radical cations of the probes. We also synthesized N-methylated analogs of $$\hbox {HPr}^{+}$$ HPr + and HE which were used in mechanistic studies. Methylation of the amine groups was not found to prevent the reaction between the radical cation of the probe and the superoxide, but it significantly increased the lifetime of the radical cation and had a substantial effect on the profiles of the oxidation products by inhibiting the formation of dimeric products. We conclude that the N-methylated analogs of HE and $$\hbox {HPr}^{+}$$ HPr + may be used as a scaffold for the design of a new generation of probes for intra- and extracellular superoxide.

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Section: Discussionsupporting

confidence: 72%

Oxidation of ethidium-based probes by biological radicals: mechanism, kinetics and implications for the detection of superoxide

Michalski

Thiebaut

Ayhan

et al. 2020

Sci Rep

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“…Therefore, for each new boronate probe developed for ONOO − detection, the reaction mechanism should be determined and product distribution quantified. The mechanism of ONOO − -derived boronate oxidation was further explored in studies on the reaction of the mitochondriatargeted probe MitoB (m-MitoPhB(OH) 2 ) and its isomers o-MitoPhB(OH) 2 and p-MitoPhB(OH) 2 with ONOO − (Sikora et al, 2013;Zielonka et al, 2015Zielonka et al, , 2016bRios et al, 2020). Similar to simple arylboronates, MitoB and its para-and orthoisomers react rapidly with ONOO − with the formation of the corresponding phenolic products at 90% reaction yield.…”

Section: Mechanism Of Oxidation Of Boronates By Onoo −mentioning

confidence: 99%

“…This intermediate undergoes hydrolysis to form phenolic product and boric acid ( Scheme 4 ). Isotope tracking experiments indicate that the oxygen atom in the phenolic product derives from the oxidant and not from the solvent (Rios et al, 2020 ).…”

Section: Chemical Reactivity Of Boronates Toward Biological Oxidantsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…The design was based on the previously reported oxidative deboronation of aryl boronates to the corresponding phenolic products ( Scheme 1A ) (Ainley and Challenger, 1930 ; Kuivila, 1954 ). Since then, boronate-based molecular probes have emerged as potential tools for detecting several biological oxidants: H 2 O 2 (Lo and Chu, 2003 ; Chang et al, 2004 ), peroxynitrite (Sikora et al, 2009 ), hypochlorous acid (Sikora et al, 2009 ), organic hydroperoxides (Michalski et al, 2014 ), and peroxymonocarbonate (Truzzi and Augusto, 2017 ; Rios et al, 2020 ). This relatively simple oxidation reaction has been utilized in the design of a wide variety of redox probes, with the detection modalities including spectrophotometry (Lo and Chu, 2003 ; Zhan et al, 2010 ; Lu et al, 2011 ; Choudhury et al, 2019 ), fluorescence (Chang et al, 2004 ; Miller et al, 2005 , 2007 ; Dickinson et al, 2010 ; Zielonka et al, 2012b ), chemiluminescence (Green et al, 2017a , b ; Seven et al, 2017 ; Gnaim and Shabat, 2019 ; Calabria et al, 2020 ), bioluminescence (Van De Bittner et al, 2010 ; Wu et al, 2014 ; Szala et al, 2020 ), high-performance liquid chromatography (HPLC) (Sikora et al, 2009 , 2013 ; Zielonka et al, 2014 ), mass spectrometry (Cochemé et al, 2011 ; Zielonka et al, 2016b ), and PET (positron emission tomography) imaging (Carroll et al, 2014 ).…”

Section: Introductionmentioning

confidence: 99%

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Boronate-Based Probes for Biological Oxidants: A Novel Class of Molecular Tools for Redox Biology

et al. 2020

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Boronate-based molecular probes are emerging as one of the most effective tools for detection and quantitation of peroxynitrite and hydroperoxides. This review discusses the chemical reactivity of boronate compounds in the context of their use for detection of biological oxidants, and presents examples of the practical use of those probes in selected chemical, enzymatic, and biological systems. The particular reactivity of boronates toward nucleophilic oxidants makes them a distinct class of probes for redox biology studies. We focus on the recent progress in the design and application of boronate-based probes in redox studies and perspectives for further developments.

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Pro‐fluorescent probe with morpholine moiety and its reactivity towards selected biological oxidants

Modrzejewska,

Grzelakowska,

Szala

et al. 2024

Luminescence

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Biologial oxidants participate in many processes in the human body. Their excessive production causes organelle damage, which may result in the accumulation of cytotoxic mediators and cell degradation and may manifest itself in various diseases. Peroxynitrite (ONOO−), hypochlorous acid (HOCl), hydrogen peroxide (H2O2), and peroxymonocarbonate (HOOCO2−) are important oxidants in biology, toxicology, and various pathologies. Derivatives of coumarin, containing an oxidant‐sensitive boronate group, have been recently developed for the fluorescent detection of inflammatory oxidants. Here, we report the synthesis and characterization of 4‐[2‐(morpholin‐4‐yl)‐2‐oxoethyl]‐2‐oxo‐2H‐chromen‐7‐yl boronic acid (MpC‐BA) as a fluorescent probe for the detection of oxidants, with better solubility in water, high stability and fast response time toward peroxynitrite and hypochlorous acid. The effectiveness of the MpC‐BA probe for the detection of peroxynitrite was measured by adding bolus ONOO− or using the co‐generating superoxide and nitrogen oxide system. MpC‐BA is oxidized by ONOO− to 7‐hydroxy‐4‐[2‐(morpholin‐4‐yl)‐2‐oxoethyl]‐2H‐chromen‐2‐one (MpC‐OH). However, peroxynitrite‐specific product (MpC‐H) is formed in the minor reaction pathway. MpC‐OH is also yielded in the reaction of MpC‐BA with HOCl, and the subsequent formation of a chlorinated MpC‐OH gives a specific product for HOCl (MpC‐OHCl). H2O2 slowly oxidizes MpC‐BA. However, the addition of NaHCO3 increased the MpC‐OH formation rate. We conclude that MpC‐BA is potentially an improved fluorescent probe detecting peroxynitrite and hypochlorite in biological settings. Complementation of the fluorescence measurements by HPLC‐based identification of chlorinated and reduced coumarin(s) will help identify the oxidants detected.

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Tracking isotopically labeled oxidants using boronate-based redox probes

Cited by 18 publications

References 86 publications

Oxidation of ethidium-based probes by biological radicals: mechanism, kinetics and implications for the detection of superoxide

Oxidation of ethidium-based probes by biological radicals: mechanism, kinetics and implications for the detection of superoxide

Boronate-Based Probes for Biological Oxidants: A Novel Class of Molecular Tools for Redox Biology

Pro‐fluorescent probe with morpholine moiety and its reactivity towards selected biological oxidants

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