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Induced fit activity-based sensing: a mechanistic study of pyrophosphate detection with a “flexible” Fe-salen complex
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, [Fe(III){salenMeCl(2)(SO(3))(2)}OH(2)](−) for pyrophosphate (PPi) detection. In the presence of PPi as an analyte,...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8477187/ https://www.ncbi.nlm.nih.gov/pubmed/34603734 http://dx.doi.org/10.1039/d1qi00209k |
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author | Yadav, Prerna Blacque, Olivier Roodt, Andreas Zelder, Felix |
author_facet | Yadav, Prerna Blacque, Olivier Roodt, Andreas Zelder, Felix |
author_sort | Yadav, Prerna |
collection | PubMed |
description | 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, [Fe(III){salenMeCl(2)(SO(3))(2)}OH(2)](−) for pyrophosphate (PPi) detection. In the presence of PPi as an analyte, the probe disassembles into its molecular subunits and releases a fluorescent signal. Our studies illustrate that the aqua form of the complex (1-OH2) is the active species and that upon substitution of Fe-coordinated H(2)O and an initial end-on coordination of HP(2)O(7)(3−), the “trapped” pyrophosphate species switches from a monodentate to a bidentate coordination mode (i.e. linkage isomerism) via a probable equilibrium process. The elusive intermediate is further stabilized by a hydrogen bonding interaction that activates the probe for the subsequent final irreversible rate-limiting step, and allows selective discrimination between the other pyrophosphate (H(2)P(2)O(7)(2−) and P(2)O(7)(4−)) species in favour of the HP(2)O(7)(3−). The flexible mode of molecular recognition and binding of HP(2)O(7)(3−) by the tetradentate probe 1-OH2 is unexpected and most effective at physiological pH, and has precedence in enzymatic catalysis (i.e. induced fit principle). These binding properties explain the previously observed outstanding selectivity of 1-OH2 for pyrophosphate over other (poly)oxophosphates and potentially competing analytes. |
format | Online Article Text |
id | pubmed-8477187 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-84771872021-10-01 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 Inorg Chem Front Chemistry 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, [Fe(III){salenMeCl(2)(SO(3))(2)}OH(2)](−) for pyrophosphate (PPi) detection. In the presence of PPi as an analyte, the probe disassembles into its molecular subunits and releases a fluorescent signal. Our studies illustrate that the aqua form of the complex (1-OH2) is the active species and that upon substitution of Fe-coordinated H(2)O and an initial end-on coordination of HP(2)O(7)(3−), the “trapped” pyrophosphate species switches from a monodentate to a bidentate coordination mode (i.e. linkage isomerism) via a probable equilibrium process. The elusive intermediate is further stabilized by a hydrogen bonding interaction that activates the probe for the subsequent final irreversible rate-limiting step, and allows selective discrimination between the other pyrophosphate (H(2)P(2)O(7)(2−) and P(2)O(7)(4−)) species in favour of the HP(2)O(7)(3−). The flexible mode of molecular recognition and binding of HP(2)O(7)(3−) by the tetradentate probe 1-OH2 is unexpected and most effective at physiological pH, and has precedence in enzymatic catalysis (i.e. induced fit principle). These binding properties explain the previously observed outstanding selectivity of 1-OH2 for pyrophosphate over other (poly)oxophosphates and potentially competing analytes. The Royal Society of Chemistry 2021-06-08 /pmc/articles/PMC8477187/ /pubmed/34603734 http://dx.doi.org/10.1039/d1qi00209k Text en This journal is © the Partner Organisations https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Yadav, Prerna Blacque, Olivier Roodt, Andreas Zelder, Felix Induced fit activity-based sensing: a mechanistic study of pyrophosphate detection with a “flexible” Fe-salen complex |
title | Induced fit activity-based sensing: a mechanistic study of pyrophosphate detection with a “flexible” Fe-salen complex |
title_full | Induced fit activity-based sensing: a mechanistic study of pyrophosphate detection with a “flexible” Fe-salen complex |
title_fullStr | Induced fit activity-based sensing: a mechanistic study of pyrophosphate detection with a “flexible” Fe-salen complex |
title_full_unstemmed | Induced fit activity-based sensing: a mechanistic study of pyrophosphate detection with a “flexible” Fe-salen complex |
title_short | Induced fit activity-based sensing: a mechanistic study of pyrophosphate detection with a “flexible” Fe-salen complex |
title_sort | induced fit activity-based sensing: a mechanistic study of pyrophosphate detection with a “flexible” fe-salen complex |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8477187/ https://www.ncbi.nlm.nih.gov/pubmed/34603734 http://dx.doi.org/10.1039/d1qi00209k |
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