Fluorescent Probes for Intracellular Carbon Monoxide Detection

Walvoord, Ryan R.; Schneider, Morgan R.; Michel, Brian W.

doi:10.1002/9781119783435.ch18

Cited by 7 publications

(14 citation statements)

References 111 publications

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“…First, CORM-3 is chemically reactive and is a far stronger reducing agent than CO at ambient temperature. , There have already been similar cases reported, ,− in which the stated “fluorescent probes for CO” turned out to only sense the CORM used as the CO source, but not CO itself. As such, there is a consensus in the field that the development of CO probes needs to use an unambiguous source of CO for assessing the “fluorescent CO probes.” In this particular publication, only the highly reactive CORM-3 was used as the CO source, leaving open many possibilities. Second, the proposed mechanism for this fluorescent probe to sense CO is not consistent with known chemistry.…”

Section: Resultsmentioning

confidence: 89%

“…With the establishment of the endogenous production of carbon monoxide (CO) through heme degradation by heme oxygenases − and the validation of its various pharmacological functions, , there comes the need for developing fluorescent probes and/or sensors for CO for highly sensitive and highly selective detection in solution, in cell culture, and tissues . Along this line, Chang and colleagues pioneered an innovative approach by cleverly taking advantage of Pd-mediated carbonylation chemistry for CO sensing .…”

Section: Introductionmentioning

confidence: 99%

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Sensing a CO-Releasing Molecule (CORM) Does Not Equate to Sensing CO: The Case of DPHP and CORM-3

2023

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Carbon monoxide (CO) is an endogenous signaling molecule with demonstrated pharmacological effects. For studying CO biology, there is a need for sensitive and selective fluorescent probes for CO as research tools. In developing such probes, CO gas and/or commercially available metal-carbonyl-based “CO-releasing molecules” (CORMs) have been used as CO sources. However, new findings are steadily emerging that some of these commonly used CORMs do not release CO reliably in buffers commonly used for studying such CO probes and have very pronounced chemical reactivities of their own, which could lead to the erroneous identification of “CO probes” that merely detect the CORM used, not CO. This is especially true when the CO-sensing mechanism relies on chemistry that is not firmly established otherwise. Cu2+ can quench the fluorescence of an imine-based fluorophore, DPHP, presumably through complexation. The Cu2+-quenched fluorescence was restored through the addition of CORM-3, a Ru-based CORM. This approach was reported as a new “strategy for detecting carbon monoxide” with the proposed mechanism being dependent on CO reduction of Cu2+ to Cu1+ under near-physiological conditions (Anal. Chem.2022941129811306). The study only used CORM-3 as the source of CO. CORM-3 has been reported to have very pronounced redox reactivity and is known not to release CO in an aqueous solution unless in the presence of a strong nucleophile. To assess whether the fluorescent response of the DPHP-Cu(II) cocktail to CORM-3 was truly through detecting CO, we report experiments using both pure CO and CORM-3. We confirm the reported DPHP-Cu(II) response to CORM-3 but not pure CO gas. Further, we did not observe the stated selectivity of DPHP for CO over sulfide species. Along this line, we also found that a reducing agent such as ascorbate was able to induce the same fluorescent turn-on as CORM-3 did. As such, the DPHP-Cu(II) system is not a CO probe and cannot be used to study CO biology. Corollary to this finding, it is critical that future work in developing CO probes uses more than a chemically reactive “CO donor” as the CO source. Especially important will be to confirm the ability of the “CO probe” to detect CO using pure CO gas or another source of CO.

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Section: Resultsmentioning

confidence: 89%

Section: Introductionmentioning

confidence: 99%

Sensing a CO-Releasing Molecule (CORM) Does Not Equate to Sensing CO: The Case of DPHP and CORM-3

2023

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“…The second approach is to use chemical probes. For example, a cyclodextrin-encapsulated iron(II) porphyrin analogue hemoCD1 has been demonstrated to be a powerful chromogenic sensor for determining CO in biological samples by a UV–vis method. , Established fluorescent probe approaches include a genetically encoded CO sensing protein (COser) and small molecule reaction-based CO probes (Figure A). − There are two major strategies for designing reaction-based fluorescent probes. ,, One is to incorporate a transition metal (such as Pd) in a fluorophore, leading to fluorescence quenching . Through the reaction with CO, Pd is removed by either palladium-mediated carbonylation or protonolysis .…”

Section: Introductionmentioning

confidence: 99%

“…Through the reaction with CO, Pd is removed by either palladium-mediated carbonylation or protonolysis . This “dequenching” strategy has been utilized in designing CO probes such as COP-1 and its analogues as well as CC-CO, among others. , The other strategy is to use an allyl group to cage the fluorophore, which can be removed via the Tsuji–Trost reaction by Pd(0) generated from Pd(II) and CO. These CO probes, especially COP-1, have been extensively used in cellular imaging-based studies and have tremendously aided studies of CO biology.…”

Section: Introductionmentioning

confidence: 99%

De Novo Construction of Fluorophores via CO Insertion-Initiated Lactamization: A Chemical Strategy toward Highly Sensitive and Highly Selective Turn-On Fluorescent Probes for Carbon Monoxide

et al. 2022

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Extensive studies in the last few decades have led to the establishment of CO as an endogenous signaling molecule and subsequently to the exploration of CO’s therapeutic roles. In the current state, there is a critical conundrum in CO-related research: the extensive knowledge of CO’s biological effects and yet an insufficient understanding of the quantitative correlations between the CO concentration and biological responses of various natures. This conundrum is partially due to the difficulty in examining precise concentration–response relationships of a gaseous molecule. Another reason is the need for appropriate tools for the sensitive detection and concentration determination of CO in the biological system. We herein report a new chemical approach to the design of fluorescent CO probes through de novo construction of fluorophores by a CO insertion-initiated lactamization reaction, which allows for ultra-low background and exclusivity in CO detection. Two series of CO detection probes have been designed and synthesized using this strategy. Using these probes, we have extensively demonstrated their utility in quantifying CO in blood, tissue, and cell culture and in cellular imaging of CO from exogenous and endogenous sources. The probes described will enable many biology and chemistry labs to study CO’s functions in a concentration-dependent fashion with very high sensitivity and selectivity. The chemical and design principles described will also be applicable in designing fluorescent probes for other small molecules.

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“…[13] Since this initial report, a number of related strategies have been developed, all of which require a transition metal for CO detection. [14] Similar to carbon monoxide, an alkene is capable of both acting as a Lewis base, donating electrons from the filled πbond to an empty orbital on the metal, and accepting electrons into the π* orbital from the transition metal via π-backbonding (Figure 2C). The model for describing this dual mode of metalligand bonding is known as the Dewar-Chatt-Duncanson model.…”

Section: Introductionmentioning

confidence: 99%

Detection of Ethylene with Defined Metal Complexes: Strategies and Recent Advances

Jensen

Michel

2022

Analysis & Sensing

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Despite its relative simplicity, ethylene is an interesting molecule with wide‐ranging impact in modern chemistry and biology. Stemming from ethylene's role as a critical plant hormone, there has been significant effort to develop selective and sensitive molecular sensors for ethylene. Late transition metal complexes have played an important role in detection strategies due to ethylene's lack of structural complexity and limited reactivity. Two main approaches to ethylene detection are identified: (1) coordination‐based sensors, wherein ethylene binds reversibly to a metal center, and (2) activity‐based sensors, wherein ethylene undergoes a reaction at a metal center, resulting in the formation and destruction of covalent bonds. Herein, we describe the advantages and disadvantages of various approaches, and the challenges remaining for sensor development.

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Fluorescent Probes for Intracellular Carbon Monoxide Detection

Cited by 7 publications

References 111 publications

Sensing a CO-Releasing Molecule (CORM) Does Not Equate to Sensing CO: The Case of DPHP and CORM-3

Sensing a CO-Releasing Molecule (CORM) Does Not Equate to Sensing CO: The Case of DPHP and CORM-3

De Novo Construction of Fluorophores via CO Insertion-Initiated Lactamization: A Chemical Strategy toward Highly Sensitive and Highly Selective Turn-On Fluorescent Probes for Carbon Monoxide

Detection of Ethylene with Defined Metal Complexes: Strategies and Recent Advances

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