Induced fit activity-based sensing: a mechanistic study of pyrophosphate detection with a “flexible” Fe-salen complex

Yadav, Prerna; Blacque, Olivier; Roodt, Andreas; Zelder, Felix

doi:10.1039/d1qi00209k

Cited by 9 publications

(26 citation statements)

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“…For long time, the selectivity of 11 for PPi over ATP and other potential interferents posed a riddle. This mystery was tackled by Zelder, Roodt and coworkers in detailed kinetic studies with absorbance and fluorescence spectroscopy supported by computational studies [72] . Overall, the PPi‐induced disassembly follows a pseudo‐first order reaction with a half‐life of ca.…”

Section: Mechanism Of Disassembly Of Fe(iii)‐salen Complexesmentioning

confidence: 99%

“…The overall disassembly reaction consists of two subsequent equilibria and one final irreversible reaction (Figure 10). [72] …”

Section: Mechanism Of Disassembly Of Fe(iii)‐salen Complexesmentioning

confidence: 99%

“…The design of a “covalent‐disassembly“ based‐probe is best performed in six steps (Figure 13; sections 9.1–9.6) according to the experience of the author‘s laboratory [20–24,31,49,72] …”

Section: Design Principlesmentioning

confidence: 99%

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“Covalent‐Disassembly”‐Based Approaches For Sensing Applications

Zelder

2024

Chemistry A European J

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The detection of analytes with small molecular probes is crucial for the analysis and understanding of chemical, medicinal, environmental and biological situations as well as processes. Classic detection approaches rely on the concept of molecular recognition and bond formation reactions. Bond breakage reactions have been less explored in similar contexts. This concept article introduces metal‐salen and metal‐imine complexes as “covalent‐disassembly”‐based (DB)‐probes for detecting polyoxophosphates, thiols, amino acids, HCN and changes in pH. It discusses the roles, importance and combinations of structurally functionalized molecular building blocks in the construction of DB‐probes. Applications of optimized DB‐probes for analyte detection in live cells and foodstuff are also discussed. Furthermore, the mechanism of the disassembly of a Fe(III)‐salen probe upon pyrophosphate binding is presented. Extraordinary selectivity for this analyte was achieved by a multistep disassembly sequence including an unprecedented structural change of the metal complex (i.e. “induced‐fit” principle). Design principles of probes for sensing applications following the “covalent‐disassembly” approach are summarized, which will help improving current systems, but will also facilitate the development of new DB‐probes for challenging analytic targets.

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Section: Mechanism Of Disassembly Of Fe(iii)‐salen Complexesmentioning

confidence: 99%

“…The overall disassembly reaction consists of two subsequent equilibria and one final irreversible reaction (Figure 10). [72] …”

Section: Mechanism Of Disassembly Of Fe(iii)‐salen Complexesmentioning

confidence: 99%

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“Covalent‐Disassembly”‐Based Approaches For Sensing Applications

Zelder

2024

Chemistry A European J

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“…Recently, an alternative sensing approach combining the well-known displacement assay (i.e., displacement of the metal cation upon PPi binding) [10,14] to a ligand hydrolysis reaction, has been developed. Thus, Zelder and co-workers pioneered metal-salen-based probes that detect PPi anions via a "turn-on" fluorogenic response arising from a molecular disassembly process that releases fluorescent salicylaldehyde [15][16][17][18][19], [20] (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

“…H-,13 C and19 F NMR spectra were recorded on a Bruker Avance 400 MHz spectrometer.Chemical shifts (d) were reported in ppm and residual non-deuterated solvent peaks were used as internal reference (proton d = 7.26 and carbon d = 77.16 for CDCl3, proton d = 2.50 and carbon d = 39.52 for DMSO-d6, and proton d = 3.31 and carbon d = 49.00 for CD3OD)[30].No internal standard was used for 19 F{ 1 H} NMR. 1 H NMR coupling constants (J) are reported in Hertz (Hz).…”

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confidence: 99%

Structural investigation of Fe(III)-salen complexes as "turn-on" fluorogenic probes for selective detection of pyrophosphate ions

Tay

Richard³

et al. 2022

Preprint

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In this work, we revisited the disassembly approach (also known as the Zelder's approach) recently proposed for sensing pyrophosphate (PPi) in water and based on the decomposition of metal-salen complexes. A systematic study devoted to the structural optimization of this novel class of PPi-responsive fluorogenic probes was conducted. Screening of eight different vicinal diamines (i.e., bridge of the salen ligand) combined with the use of 8-formyl-7-hydroxycoumarin (i.e., salicylaldehyde derivative) as the fluorescent reporter, has led to a set of novel and fully characterized coumarin-salen Fe(III) complexes. A series of analytical validations helped us to identify that coumarin-salen Fe(III) complexes derived from ethylenediamine and racemic 1,2-propylenediamine backbones exhibit the best and selective PPi-sensing performances (the limits of detection were estimated as 3.15 × 10-6 M and 2.81 × 10-6 M respectively). The implementation of both fluorescence time-course measurements and RP-HPLC-fluorescence analyses has enabled us to gain further insights into the disassembly-based probes' activation mechanism. This study therefore contributes to demonstrate that the disassembly approach is a valuable strategy to achieve fluorogenic activity-based sensing of anions.

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Revisiting the Chemistry and Photophysics of 3‐(N‐Methylpyridinium‐4‐yl)Coumarins for Designing “Covalent‐Assembly” and “Molecular Disassembly” Fluorescent Probes**

Gaumerd,

Renault,

Renard

et al. 2024

ChemPhotoChem

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The constant need for high‐performance aniline‐ or phenol‐based fluorophores suitable for the construction of activity‐based fluorescent probes, led us to study both synthesis and photophysics of C3‐N‐methylpyridinium‐4‐yl substituted 7‐(dialkylamino)/7‐hydroxycoumarins. Indeed, in the field of photoactive organic molecules, the positively charged N‐alkylpyridinium‐4‐yl groups are often used as acceptor units to dramatically impact spectral features through promoting intramolecular charge transfer (ICT) processes. They are also known as effective water‐solubilizing and mitochondria targeting moieties. The poor fluorescence efficiency of cationic 7‐hydroxycoumarin derivatives in aqueous physiological conditions was highlighted and rationalized by the predominance of a neutral quinonoid form in such buffer medium. The ability of the excited singlet state (S1) of this neutral species to undergo intersystem crossing (ISC) to triplet state (T1) was partly supported by phosphorescence measurements of singlet oxygen. We also took advantage of green‐emissive properties of 7‐(diethylamino)‐3‐(N‐methylpyridinium‐4‐yl)coumarin to successfully design and validate a novel small‐molecule fluorescent probe for the detection of alkaline phosphatase (ALP), based on the "covalent‐assembly" principle. A practical use of ortho‐formylated 7‐hydroxy‐3‐(N‐methylpyridinium‐4‐yl)coumarin was next considered with the synthesis of a Fe(III)‐salen complex whose the potential as a "molecular disassembly" probe for fluorogenic sensing of pyrophosphate (PPi) anion was assessed.

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Induced fit activity-based sensing: a mechanistic study of pyrophosphate detection with a “flexible” Fe-salen complex

Abstract: Activity-based sensing of biological targets is attracting increasing attention. In this work, we report detailed UV-Vis and fluorescence mechanistic studies on an Fe-salen based probe, [FeIII{salenMeCl2(SO3)2}OH2]- for pyrophosphate (PPi) detection....

Cited by 9 publications

References 56 publications

“Covalent‐Disassembly”‐Based Approaches For Sensing Applications

“Covalent‐Disassembly”‐Based Approaches For Sensing Applications

Structural investigation of Fe(III)-salen complexes as "turn-on" fluorogenic probes for selective detection of pyrophosphate ions

Revisiting the Chemistry and Photophysics of 3‐(N‐Methylpyridinium‐4‐yl)Coumarins for Designing “Covalent‐Assembly” and “Molecular Disassembly” Fluorescent Probes**

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