Harnessing chemical exchange: <sup>19</sup>F magnetic resonance OFF/ON zinc sensing with a Tm(<scp>iii</scp>) complex

Yu, Meng; Xie, Da; Kadakia, Rahul T.; Wang, Weiran; Que, Emily L.

doi:10.1039/d0cc01876g

Cited by 15 publications

(70 citation statements)

References 36 publications

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“…In yet another approach, Yu et al used a thulium-based agent with a DO3A core, a pyridine chelate, and a perfluoro-tert-butyl tag which was only visible by 19 F NMR in the presence of Zn 2+ . The authors concluded that this signal results from slower chemical exchange upon Zn 2+ binding, which leads to a rigid conformation of the Zn 2+ chelator [ 68 ]. Other thulium-based sensors have also been reported [ 69 ].…”

Section: Detection Of Zinc With Magnetic Resonance Imagingmentioning

confidence: 99%

Imaging Tissue Physiology In Vivo by Use of Metal Ion-Responsive MRI Contrast Agents

2020

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Paramagnetic metal ion complexes, mostly based on gadolinium (Gd3+), have been used for over 30 years as magnetic resonance imaging (MRI) contrast agents. Gd3+-based contrast agents have a strong influence on T1 relaxation times and are consequently the most commonly used agents in both the clinical and research environments. Zinc is an essential element involved with over 3000 different cellular proteins, and disturbances in tissue levels of zinc have been linked to a wide range of pathologies, including Alzheimer’s disease, prostate cancer, and diabetes mellitus. MR contrast agents that respond to the presence of Zn2+ in vivo offer the possibility of imaging changes in Zn2+ levels in real-time with the superior spatial resolution offered by MRI. Such responsive agents, often referred to as smart agents, are typically composed of a paramagnetic metal ion with a ligand encapsulating it and one or more chelating units that selectively bind with the analyte of interest. Translation of these agents into clinical radiology is the next goal. In this review, we discuss Gd3+-based MR contrast agents that respond to a change in local Zn2+ concentration.

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Section: Detection Of Zinc With Magnetic Resonance Imagingmentioning

confidence: 99%

Imaging Tissue Physiology In Vivo by Use of Metal Ion-Responsive MRI Contrast Agents

2020

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“…TmL13 (Scheme 4) functions as an off/on probe for Zn 2+ detection. [23] In the absence of Zn 2+ , the system is highly flexible and no 19 F signal is observed. Upon Zn 2+ coordination, one major and three minor signals appear corresponding to different diastereoisomers of the probe.…”

Section: Other Ln 3+ -Based Contrast Agents: Paracest Parashift and 19 F Contrast Agentsmentioning

confidence: 99%

Metal-based environment-sensitive MRI contrast agents

Bonnet

Tóth²

2021

Current Opinion in Chemical Biology

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“…Responsive paramagnetic complexes have also flourished, particularly based on transition metal ions for redox or pH sensing [80]. Recently, a Tm 3+ complex, TmPFZ-1 bearing nine fluorine atoms on the DPA moiety was developed by Que et al (Figure 11) [81]. In the absence of Zn 2+ , the system is highly flexible and the probe is not detectable by 19 F MRI.…”

Section: F Mri Probesmentioning

confidence: 99%

From Zn(II) to Cu(II) Detection by MRI Using Metal-Based Probes: Current Progress and Challenges

2020

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Zinc and copper are essential cations involved in numerous biological processes, and variations in their concentrations can cause diseases such as neurodegenerative diseases, diabetes and cancers. Hence, detection and quantification of these cations are of utmost importance for the early diagnosis of disease. Magnetic resonance imaging (MRI) responsive contrast agents (mainly Lanthanide(+III) complexes), relying on a change in the state of the MRI active part upon interaction with the cation of interest, e.g., switch ON/OFF or vice versa, have been successfully utilized to detect Zn2+ and are now being developed to detect Cu2+. These paramagnetic probes mainly exploit the relaxation-based properties (T1-based contrast agents), but also the paramagnetic induced hyperfine shift properties (paraCEST and parashift probes) of the contrast agents. The challenges encountered going from Zn2+ to Cu2+ detection will be stressed and discussed herein, mainly involving the selectivity of the probes for the cation to detect and their responsivity at physiologically relevant concentrations. Depending on the response mechanism, the use of fast-field cycling MRI seems promising to increase the detection field while keeping a good response. In vivo applications of cation responsive MRI probes are only in their infancy and the recent developments will be described, along with the associated quantification problems. In the case of relaxation agents, the presence of another method of local quantification, e.g., synchrotron X-Ray fluorescence, single-photon emission computed tomography (SPECT) or positron emission tomography (PET) techniques, or 19F MRI is required, each of which has its own advantages and disadvantages.

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Harnessing chemical exchange: ¹⁹F magnetic resonance OFF/ON zinc sensing with a Tm(iii) complex

Abstract: A Tm(iii) complex displays an “off–on” 19F NMR/MRI response to Zn(ii) upon tuning the chemical exchange rate.

Cited by 15 publications

References 36 publications

Imaging Tissue Physiology In Vivo by Use of Metal Ion-Responsive MRI Contrast Agents

Imaging Tissue Physiology In Vivo by Use of Metal Ion-Responsive MRI Contrast Agents

Metal-based environment-sensitive MRI contrast agents

From Zn(II) to Cu(II) Detection by MRI Using Metal-Based Probes: Current Progress and Challenges

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Harnessing chemical exchange: 19F magnetic resonance OFF/ON zinc sensing with a Tm(iii) complex

Abstract: A Tm(iii) complex displays an “off–on” 19F NMR/MRI response to Zn(ii) upon tuning the chemical exchange rate.

Cited by 15 publications

References 36 publications

Imaging Tissue Physiology In Vivo by Use of Metal Ion-Responsive MRI Contrast Agents

Imaging Tissue Physiology In Vivo by Use of Metal Ion-Responsive MRI Contrast Agents

Metal-based environment-sensitive MRI contrast agents

From Zn(II) to Cu(II) Detection by MRI Using Metal-Based Probes: Current Progress and Challenges

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Harnessing chemical exchange: ¹⁹F magnetic resonance OFF/ON zinc sensing with a Tm(iii) complex