19F NMR: An underused efficient probe for paramagnetic metal centers in bioinorganic solution chemistry

Belle, Catherine; Béguin, Claude; Hamman, Sylvain; Pierre, Jean‐Louis

doi:10.1016/j.ccr.2008.06.015

Cited by 19 publications

(18 citation statements)

References 54 publications

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“…The inequality R 1b ) R 1f results from the hypothesis that, when the ligand L is bound to Gd 3 + , the distance r I between this ion and the studied nuclear spin I is short enough for their dipolar coupling to be strong and give rise to a high relaxation rate R 1M much larger than the relaxation rate R 1f in the f state given by Equation (6). Then according to Equation (3), we have…”

Section: General Relaxivity Properties In the Presence Of Several Ligmentioning

confidence: 94%

“…Its application to investigate paramagnetic centres in bioinorganic solution chemistry was reviewed recently. [6] In magnetic resonance imaging (MRI), it was proposed to image lanthanide Ln 3 + complexes carrying 19 F reporters of short longitudinal relaxation times. [7,8] Among paramagnetic centres, Ln 3 + ions have attracted much attention in past years owing to their nearly identical chemistry and versatile magnetic properties.…”

Section: Introductionmentioning

confidence: 99%

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Paramagnetic Relaxation Enhancements in Acetate and Its Fluorine Derivatives Interacting with Gd³⁺: Complex Formation, Structure, and Transmetallation

Bonnet¹,

Fries²

2010

ChemPhysChem

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The relative spatial distribution and motion with respect to Gd(3+) of the (1)H and (19)F nuclei in the acetate ion and its fluorine derivatives are studied in D(2)O solutions through the paramagnetic relaxation rate enhancements (PREs) of these nuclei. We derive general theoretical expressions of the longitudinal PRE in terms of the analytical concentrations of metal and ligands, formation constants of the complexes, metal-nucleus distances, and coordination lifetimes of the ligands. The observed formation constants of the 1 metal: 1 ligand complexes markedly decrease with increasing number of fluorine atoms, the electronegativity of which reduces the negative partial charge of the coordinating COO(-) group. The coordination lifetimes are very short at the scale of the relaxation times of the protons of metal bound acetate, that is, shorter than about 10 μs. The average distance of the acetate protons from Gd(3+) is in fair agreement with independent crystallographic determination. The release of free Gd(3+) from the very stable Gddtpa (dtpa=diethylene-triaminepentaacetate) complex caused by the competition of Zn(2+) for dtpa, is evidenced by an increase of the PREs with Zn(2+) concentration. The observed PRE increase is consistent with the known equilibrium constants governing the speciation involving Gd(3+), Zn(2+), and dtpa. The present case study illustrates a method which easily yields experimental tunable properties suitable to test the ongoing theories of lanthanide Ln(3+) complexation in solution.

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Section: General Relaxivity Properties In the Presence Of Several Ligmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

Paramagnetic Relaxation Enhancements in Acetate and Its Fluorine Derivatives Interacting with Gd³⁺: Complex Formation, Structure, and Transmetallation

Bonnet¹,

Fries²

2010

ChemPhysChem

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“…In addition to the intrinsic fluorescence of the porphyrinoids, magnetic resonance of fluorinated compounds ( 19 F-NMR), 70–72 18 F positron emission topology (PET) imaging, 13,73 carbon– fluorine spectroscopy (CFR), 16 and fluoro-Raman spectroscopy (FRS) 74 are all enabled for sensitive and minimally invasive imaging of disease or as sensors.…”

Section: Substituted Fluorinated Porphyrinoids For Biological Applicamentioning

confidence: 99%

Fluorinated porphyrinoids as efficient platforms for new photonic materials, sensors, and therapeutics

et al. 2016

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Porphyrinoids are robust heterocyclic dyes studied extensively for their applications in medicine and as photonic materials because of their tunable photophysical properties, diverse means of modifying the periphery, and the ability to chelate most transition metals. Commercial applications include their use as phthalocyanine dyes in optical discs, porphyrins in photodynamic therapy, and as oxygen sensors. Most applications of these dyes require exocyclic moieties to improve solubility, target diseases, modulate photophysical properties, or direct the self-organization into architectures with desired photonic properties. The synthesis of the porphyrinoid depends on the desired application, but the de novo synthesis often involves several steps, is time consuming, and results in low isolated yields. Thus, the application of core porphyrinoid platforms that can be rapidly and efficiently modified to evaluate new molecular architectures allows researchers to focus on the design concepts rather than the synthesis methods, and opens porphyrinoid chemistry to a broader scientific community. We have focused on several widely available, commercially viable porphyrinoids as platforms: meso-perfluorophenylporphyrin, perfluoro-phthalocyanine, and meso-perfluorophenylcorrole. The perfluorophenylporphyrin is readily converted to the chlorin, bacteriochlorin, and isobacteriochlorin. Derivatives of all six of these core platforms can be efficiently and controllably made via mild nucleophilic aromatic substitution reactions using primary S, N, and O nucleophiles bearing a wide variety of functional groups. The remaining fluoro groups enhance the photo and oxidative stability of the dyes and can serve as spectroscopic signatures to characterize the compounds or in imaging applications using 19F NMR. This review provides an overview of the chemistry of fluorinated porphyrinoids that are being used as a platform to create libraries of photo-active compounds for applications in medicine and materials.

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“…Indeed, this has been used to identify cellular compartmentation based on the ability of the contrast agent to relax extracellular, but not intracellular material [159]. Direct relaxation can also be achieved by including F or CF 3 in a paramagnetic ligand complex [113, 160]. If 19 F is attached very close to a paramagnetic center, such as Gd 3+ or Fe 3+ , the local paramagnetic relaxation effect (PRE) can strongly influence the fluorine atom.…”

Section: Innovations and Enhancementsmentioning

confidence: 99%

New frontiers and developing applications in 19F NMR

Jian

Hallac

Chiguru

et al. 2013

Progress in Nuclear Magnetic Resonance Spectroscopy

171

161

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19F NMR: An underused efficient probe for paramagnetic metal centers in bioinorganic solution chemistry

Cited by 19 publications

References 54 publications

Paramagnetic Relaxation Enhancements in Acetate and Its Fluorine Derivatives Interacting with Gd³⁺: Complex Formation, Structure, and Transmetallation

Paramagnetic Relaxation Enhancements in Acetate and Its Fluorine Derivatives Interacting with Gd³⁺: Complex Formation, Structure, and Transmetallation

Fluorinated porphyrinoids as efficient platforms for new photonic materials, sensors, and therapeutics

New frontiers and developing applications in 19F NMR

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19F NMR: An underused efficient probe for paramagnetic metal centers in bioinorganic solution chemistry

Cited by 19 publications

References 54 publications

Paramagnetic Relaxation Enhancements in Acetate and Its Fluorine Derivatives Interacting with Gd3+: Complex Formation, Structure, and Transmetallation

Paramagnetic Relaxation Enhancements in Acetate and Its Fluorine Derivatives Interacting with Gd3+: Complex Formation, Structure, and Transmetallation

Fluorinated porphyrinoids as efficient platforms for new photonic materials, sensors, and therapeutics

New frontiers and developing applications in 19F NMR

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Product

Resources

About

Paramagnetic Relaxation Enhancements in Acetate and Its Fluorine Derivatives Interacting with Gd³⁺: Complex Formation, Structure, and Transmetallation

Paramagnetic Relaxation Enhancements in Acetate and Its Fluorine Derivatives Interacting with Gd³⁺: Complex Formation, Structure, and Transmetallation