Responsive fluorinated lanthanide probes for 19F magnetic resonance spectroscopy

Senanayake, P. Kanthi; Kenwright, Alan M.; Parker, David; Hoorn, Susanna K. van der

doi:10.1039/b705844f

Cited by 54 publications

(101 citation statements)

References 22 publications

(7 reference statements)

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“…However, one study illustrated a measurable relaxation effect of Gd on aqueous 19 F, suggesting that proximity of the Gd atoms to the 19 F nuclei may be the critical factor for such a hypothetical interaction (11). A more recent study utilizing various fluorine‐lanthanide complexes has verified that placing the lanthanide close to the fluorine nucleus results in shortened T 1 times and increases the sensitivity for NMR studies (12).…”

mentioning

confidence: 99%

Gadolinium‐modulated ¹⁹F signals from perfluorocarbon nanoparticles as a new strategy for molecular imaging

Neubauer¹,

Myerson²,

Caruthers

et al. 2008

Magnetic Resonance in Med

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Recent advances in the design of fluorinated nanoparticles for molecular magnetic resonance imaging (MRI) have enabled specific detection of 19 F nuclei, providing unique and quantifiable spectral signatures. However, a pressing need for signal enhancement exists because the total 19 F in imaging voxels is often limited. By directly incorporating a relaxation agent, gadolinium (Gd), into the lipid monolayer that surrounds the perfluorocarbon (PFC), a marked augmentation of the 19 F signal from 200-nm nanoparticles was achieved. This design increases the magnetic relaxation rate of the 19 F nuclei fourfold at 1.5 T and effects a 125% increase in signal-an effect that is maintained when they are targeted to human plasma clots. By varying the surface concentration of Gd, the relaxation effect can be quantitatively modulated to tailor particle properties. This novel strategy dramatically improves the sensitivity and range of 19

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mentioning

confidence: 99%

Gadolinium‐modulated ¹⁹F signals from perfluorocarbon nanoparticles as a new strategy for molecular imaging

Neubauer¹,

Myerson²,

Caruthers

et al. 2008

Magnetic Resonance in Med

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“…Recently, we introduced a new class of compound where the 19 F relaxation is manipulated by combining the relaxing lanthanide centre and the 19 F group within the same molecule (15)(16)(17). The 19 F relaxation rates are controlled through the choice of lanthanide and careful molecular design to determine the location of the MR active 19 F group with the lanthanide ion.…”

mentioning

confidence: 99%

¹⁹F‐lanthanide complexes with increased sensitivity for ¹⁹F‐MRI: Optimization of the MR acquisition

Chalmers

Kenwright

Parker

et al. 2011

Magnetic Resonance in Med

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Fluorine-19 magnetic resonance methods offer advantages for molecular or cellular imaging in vivo due to the absence of radioactivity, lack of naturally occurring background signal, and the ability to easily combine measurements with anatomical MRI. Previous studies have shown that 19 F-MRI sensitivity is limited to millimolar concentrations by slow longitudinal relaxation. In this study, a new class of macrocyclic fluorinated lanthanide complexes is investigated where relaxation rates are significantly shortened by proximity of the fluorine group to a paramagnetic lanthanide ion located within the same molecule. Longitudinal and transverse relaxation rates are field dependent and in the range 50-150 s 21 and 70-200 s 21 , respectively, at 7 T. Relaxation rates in these complexes are a function of the molecular structure and are independent of concentration at biologically relevant levels, so can be used as criteria to optimize imaging acquisition. Phantom experiments at 7 T indicate a lower limit for detection by imaging of 20 mM. Magn Reson Med 66:931-936,

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“…Most notably, inclusion of an optimized reporter arm can provide a second, brighter reporter signal and enable measurement of relative peak intensities or shis for improved probe performance. 15,21,22,27,29 In addition, groups for targeting or conjugation could be incorporated to improve accumulation and half-life in tissues of interest. Further evaluation of this group for the design of modular, multifunctional imaging probes in vivo pH measurement is on-going.…”

Section: Discussionmentioning

confidence: 99%

“…21,22,27 A responsive group is used to perturb the ligand eld of the metal and/or the position of the reporter group to generate a change in the chemical shi of the reporter group in response to stimuli. 15,[28][29][30] A wide variety of protic groups have been applied as responsive groups for Ln(III) pH-sensing, notably substituted phenols 10,23,31-33 and phosphates. 22,25,27 As imaging probes become increasingly multifunctional, moieties that can serve as both reporters and responsive groups are increasingly needed to enable incorporation of additional functionalities for ratiometric imaging or targeting.…”

Section: Introductionmentioning

confidence: 99%

A Ln(iii)-3-hydroxypyridine pH responsive probe optimized by DFT

et al. 2020

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Differences in tissue pH can be diagnostic of cancer and other conditions that shift cell metabolism.Paramagnetic probes are promising tools for pH mapping in vivo using magnetic resonance spectroscopy (MRS) as they provide uniquely shifted MR signals that change with pH. Here, we demonstrate a 3-hydroxy-6-methylpyridyl coordinating group as a new pH-responsive reporter group for Ln(III) MRS probes. The pH response of the complex was observed by UV-Vis, fluorescence, and NMR spectroscopies, and modeled using DFT. These results provide insight into the observed pH-dependent NMR spectrum of the complex. The protonation state of the hydroxypyridine changes the coordinating ability of the ligand, affecting the dipolar field of the lanthanide and the chemical shift of nearby reporter nuclei. The favorable pH response and coordination properties of the 3-hydroxypyridyl group indicate its potential for further development as a dual responsive-reporter group. Incorporation into optimized scaffolds for MRS detection may enable sensitive pH-mapping in vivo. † Electronic supplementary information (ESI) available: Additional gures and detailed characterization for all new compounds are included in the supporting information. SeeScheme 1 Deprotonation of HMP in Ln(III)-DO3A-HMP between pH 6 and pH 8 increases the electron density of the coordinating oxygen, perturbing the ligand field, and leading to an enhanced change in the NMR shift of the pyridyl methyl group over a diamagnetic analog due to the shifting pseuodocontact field of the lanthanide.8996 | RSC Adv., 2020, 10, 8994-8999This journal is

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Responsive fluorinated lanthanide probes for 19F magnetic resonance spectroscopy

Cited by 54 publications

References 22 publications

Gadolinium‐modulated ¹⁹F signals from perfluorocarbon nanoparticles as a new strategy for molecular imaging

Gadolinium‐modulated ¹⁹F signals from perfluorocarbon nanoparticles as a new strategy for molecular imaging

¹⁹F‐lanthanide complexes with increased sensitivity for ¹⁹F‐MRI: Optimization of the MR acquisition

A Ln(iii)-3-hydroxypyridine pH responsive probe optimized by DFT

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Responsive fluorinated lanthanide probes for 19F magnetic resonance spectroscopy

Cited by 54 publications

References 22 publications

Gadolinium‐modulated 19F signals from perfluorocarbon nanoparticles as a new strategy for molecular imaging

Gadolinium‐modulated 19F signals from perfluorocarbon nanoparticles as a new strategy for molecular imaging

19F‐lanthanide complexes with increased sensitivity for 19F‐MRI: Optimization of the MR acquisition

A Ln(iii)-3-hydroxypyridine pH responsive probe optimized by DFT

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Gadolinium‐modulated ¹⁹F signals from perfluorocarbon nanoparticles as a new strategy for molecular imaging

Gadolinium‐modulated ¹⁹F signals from perfluorocarbon nanoparticles as a new strategy for molecular imaging

¹⁹F‐lanthanide complexes with increased sensitivity for ¹⁹F‐MRI: Optimization of the MR acquisition