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Hydrazone Molecular Switches with Paramagnetic Center as (19)F Magnetic Resonance Imaging Relaxation Enhancement Agents for pH Imaging

[Image: see text] The design and synthesis of hydrazone-based switches with a CF(3) reporting group for (19)F pH imaging using relaxation rate changes were described. A paramagnetic center was introduced into the hydrazone molecular switch scaffold by substitution of an ethyl functional group with a...

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Autores principales: Janasik, Dawid, Jasiński, Krzysztof, Szreder, Julia, Węglarz, Władysław P., Krawczyk, Tomasz
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10226166/
https://www.ncbi.nlm.nih.gov/pubmed/37198734
http://dx.doi.org/10.1021/acssensors.3c00080
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author Janasik, Dawid
Jasiński, Krzysztof
Szreder, Julia
Węglarz, Władysław P.
Krawczyk, Tomasz
author_facet Janasik, Dawid
Jasiński, Krzysztof
Szreder, Julia
Węglarz, Władysław P.
Krawczyk, Tomasz
author_sort Janasik, Dawid
collection PubMed
description [Image: see text] The design and synthesis of hydrazone-based switches with a CF(3) reporting group for (19)F pH imaging using relaxation rate changes were described. A paramagnetic center was introduced into the hydrazone molecular switch scaffold by substitution of an ethyl functional group with a paramagnetic complex. The mechanism of activation relies on a gradual increase in T(1) and T(2) magnetic resonance imaging (MRI) relaxation times as pH decreases due to E/Z isomerization, which results in a change in the distance between fluorine atoms and the paramagnetic center. Among the three possible variants of the ligand, the meta isomer was found to offer the highest potential changes in relaxation rates due to the significant paramagnetic relaxation enhancement (PRE) effect and a stable position of the (19)F signal, allowing for the tracking of a single narrow (19)F resonance for imaging purposes. The selection of the most suitable Gd(III) paramagnetic ion for complexation was conducted by theoretical calculations based on the Bloch–Redfield–Wangsness (BRW) theory, taking into account the electron–nucleus dipole–dipole and Curie interactions only. The results were verified experimentally, confirming the accuracy of theoretical predictions, good solubility, and stability of the agents in water and the reversible transition between E and Z–H(+) isomers. The results demonstrate the potential of this approach for pH imaging using relaxation rate changes instead of chemical shift.
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spelling pubmed-102261662023-05-30 Hydrazone Molecular Switches with Paramagnetic Center as (19)F Magnetic Resonance Imaging Relaxation Enhancement Agents for pH Imaging Janasik, Dawid Jasiński, Krzysztof Szreder, Julia Węglarz, Władysław P. Krawczyk, Tomasz ACS Sens [Image: see text] The design and synthesis of hydrazone-based switches with a CF(3) reporting group for (19)F pH imaging using relaxation rate changes were described. A paramagnetic center was introduced into the hydrazone molecular switch scaffold by substitution of an ethyl functional group with a paramagnetic complex. The mechanism of activation relies on a gradual increase in T(1) and T(2) magnetic resonance imaging (MRI) relaxation times as pH decreases due to E/Z isomerization, which results in a change in the distance between fluorine atoms and the paramagnetic center. Among the three possible variants of the ligand, the meta isomer was found to offer the highest potential changes in relaxation rates due to the significant paramagnetic relaxation enhancement (PRE) effect and a stable position of the (19)F signal, allowing for the tracking of a single narrow (19)F resonance for imaging purposes. The selection of the most suitable Gd(III) paramagnetic ion for complexation was conducted by theoretical calculations based on the Bloch–Redfield–Wangsness (BRW) theory, taking into account the electron–nucleus dipole–dipole and Curie interactions only. The results were verified experimentally, confirming the accuracy of theoretical predictions, good solubility, and stability of the agents in water and the reversible transition between E and Z–H(+) isomers. The results demonstrate the potential of this approach for pH imaging using relaxation rate changes instead of chemical shift. American Chemical Society 2023-05-18 /pmc/articles/PMC10226166/ /pubmed/37198734 http://dx.doi.org/10.1021/acssensors.3c00080 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Janasik, Dawid
Jasiński, Krzysztof
Szreder, Julia
Węglarz, Władysław P.
Krawczyk, Tomasz
Hydrazone Molecular Switches with Paramagnetic Center as (19)F Magnetic Resonance Imaging Relaxation Enhancement Agents for pH Imaging
title Hydrazone Molecular Switches with Paramagnetic Center as (19)F Magnetic Resonance Imaging Relaxation Enhancement Agents for pH Imaging
title_full Hydrazone Molecular Switches with Paramagnetic Center as (19)F Magnetic Resonance Imaging Relaxation Enhancement Agents for pH Imaging
title_fullStr Hydrazone Molecular Switches with Paramagnetic Center as (19)F Magnetic Resonance Imaging Relaxation Enhancement Agents for pH Imaging
title_full_unstemmed Hydrazone Molecular Switches with Paramagnetic Center as (19)F Magnetic Resonance Imaging Relaxation Enhancement Agents for pH Imaging
title_short Hydrazone Molecular Switches with Paramagnetic Center as (19)F Magnetic Resonance Imaging Relaxation Enhancement Agents for pH Imaging
title_sort hydrazone molecular switches with paramagnetic center as (19)f magnetic resonance imaging relaxation enhancement agents for ph imaging
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10226166/
https://www.ncbi.nlm.nih.gov/pubmed/37198734
http://dx.doi.org/10.1021/acssensors.3c00080
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