Single (19)F Probe for Simultaneous Detection of Multiple Metal Ions Using MiCEST MRI

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2014 Dec 20

PMID 25523816

Citations 22

Authors

Amnon Bar-Shir

Nirbhay N Yadav

Assaf A Gilad

Peter C M van Zijl

Michael T McMahon

Jeff W M Bulte

Affiliations

Soon will be listed here.

Abstract

The local presence and concentration of metal ions in biological systems has been extensively studied ex vivo using fluorescent dyes. However, the detection of multiple metal ions in vivo remains a major challenge. We present a magnetic resonance imaging (MRI)-based method for noninvasive detection of specific ions that may be coexisting, using the tetrafluorinated derivative of the BAPTA (TF-BAPTA) chelate as a (19)F chelate analogue of existing optical dyes. Taking advantage of the difference in the ion-specific (19)F nuclear magnetic resonance (NMR) chemical shift offset (Δω) values between the ion-bound and free TF-BAPTA, we exploited the dynamic exchange between ion-bound and free TF-BAPTA to obtain MRI contrast with multi-ion chemical exchange saturation transfer (miCEST). We demonstrate that TF-BAPTA as a prototype single (19)F probe can be used to separately visualize mixed Zn(2+) and Fe(2+) ions in a specific and simultaneous fashion, without interference from potential competitive ions.

Citing Articles

Design Chemical Exchange Saturation Transfer Contrast Agents and Nanocarriers for Imaging Proton Exchange .

Su H, Chan K ACS Nano. 2024; 18(50):33775-33791.

PMID: 39642940 PMC: 11656841. DOI: 10.1021/acsnano.4c05923.

A Reactive and Specific Sensor for Activity-Based F-MRI Sensing of Zn.

Lee L, Tirukoti N, Subramani B, Goren E, Diskin-Posner Y, Allouche-Arnon H ACS Sens. 2024; 9(11):5770-5775.

PMID: 39445901 PMC: 11590105. DOI: 10.1021/acssensors.4c01895.

Radiofrequency labeling strategies in chemical exchange saturation transfer MRI.

Bie C, van Zijl P, Xu J, Song X, Yadav N NMR Biomed. 2023; 36(6):e4944.

PMID: 37002814 PMC: 10312378. DOI: 10.1002/nbm.4944.

Design Principles of Responsive Relaxometric F Contrast Agents: Evaluation from the Point of View of Relaxation Theory and Experimental Data.

Zalewski M, Janasik D, Wierzbicka A, Krawczyk T Inorg Chem. 2022; 61(48):19524-19542.

PMID: 36384024 PMC: 9727736. DOI: 10.1021/acs.inorgchem.2c03451.

Fast Ion-Chelate Dissociation Rate for MRI of Labile Zinc with Frequency-Specific Encodability.

Tirukoti N, Avram L, Haris T, Lerner B, Diskin-Posner Y, Allouche-Arnon H J Am Chem Soc. 2021; 143(30):11751-11758.

PMID: 34297566 PMC: 8397314. DOI: 10.1021/jacs.1c05376.

References

Cheng L, Yang K, Li Y, Chen J, Wang C, Shao M . Facile preparation of multifunctional upconversion nanoprobes for multimodal imaging and dual-targeted photothermal therapy. Angew Chem Int Ed Engl. 2011; 50(32):7385-90. DOI: 10.1002/anie.201101447. View

Yu J, Kodibagkar V, Cui W, Mason R . 19F: a versatile reporter for non-invasive physiology and pharmacology using magnetic resonance. Curr Med Chem. 2005; 12(7):819-48. DOI: 10.2174/0929867053507342. View

Tsien R . Fluorescent probes of cell signaling. Annu Rev Neurosci. 1989; 12:227-53. DOI: 10.1146/annurev.ne.12.030189.001303. View

Mamedov I, Canals S, Henig J, Beyerlein M, Murayama Y, Mayer H . In vivo characterization of a smart MRI agent that displays an inverse response to calcium concentration. ACS Chem Neurosci. 2012; 1(12):819-28. PMC: 3368642. DOI: 10.1021/cn100083a. View

London R, Rhee C, Murphy E, Gabel S, LEVY L . NMR-sensitive fluorinated and fluorescent intracellular calcium ion indicators with high dissociation constants. Am J Physiol. 1994; 266(5 Pt 1):C1313-22. DOI: 10.1152/ajpcell.1994.266.5.C1313. View

Bar-Shir A, Gilad A, Chan K, Liu G, van Zijl P, Bulte J . Metal ion sensing using ion chemical exchange saturation transfer 19F magnetic resonance imaging. J Am Chem Soc. 2013; 135(33):12164-7. PMC: 3786336. DOI: 10.1021/ja403542g. View

van Zijl P, Yadav N . Chemical exchange saturation transfer (CEST): what is in a name and what isn't?. Magn Reson Med. 2011; 65(4):927-48. PMC: 3148076. DOI: 10.1002/mrm.22761. View

Castelli D, Terreno E, Longo D, Aime S . Nanoparticle-based chemical exchange saturation transfer (CEST) agents. NMR Biomed. 2013; 26(7):839-49. DOI: 10.1002/nbm.2974. View

Lee T, Zhang X, Dhar S, Faas H, Lippard S, Jasanoff A . In vivo imaging with a cell-permeable porphyrin-based MRI contrast agent. Chem Biol. 2010; 17(6):665-73. PMC: 2906115. DOI: 10.1016/j.chembiol.2010.05.009. View

10.

Smith G, Hesketh R, Metcalfe J, Feeney J, Morris P . Intracellular calcium measurements by 19F NMR of fluorine-labeled chelators. Proc Natl Acad Sci U S A. 1983; 80(23):7178-82. PMC: 390017. DOI: 10.1073/pnas.80.23.7178. View

11.

Bar-Shir A, Avram L, Yariv-Shoushan S, Anaby D, Cohen S, Segev-Amzaleg N . Alginate-coated magnetic nanoparticles for noninvasive MRI of extracellular calcium. NMR Biomed. 2014; 27(7):774-83. DOI: 10.1002/nbm.3117. View

12.

Niers J, Chen J, Lewandrowski G, Kerami M, Garanger E, Wojtkiewicz G . Single reporter for targeted multimodal in vivo imaging. J Am Chem Soc. 2012; 134(11):5149-56. PMC: 3310895. DOI: 10.1021/ja209868g. View

13.

Lubag A, De Leon-Rodriguez L, Burgess S, Sherry A . Noninvasive MRI of β-cell function using a Zn2+-responsive contrast agent. Proc Natl Acad Sci U S A. 2011; 108(45):18400-5. PMC: 3215051. DOI: 10.1073/pnas.1109649108. View

14.

Garaschuk O, Milos R, Konnerth A . Targeted bulk-loading of fluorescent indicators for two-photon brain imaging in vivo. Nat Protoc. 2007; 1(1):380-6. DOI: 10.1038/nprot.2006.58. View

15.

Soesbe T, Wu Y, Sherry A . Advantages of paramagnetic chemical exchange saturation transfer (CEST) complexes having slow to intermediate water exchange properties as responsive MRI agents. NMR Biomed. 2012; 26(7):829-38. PMC: 3593956. DOI: 10.1002/nbm.2874. View

16.

Kotera N, Tassali N, Leonce E, Boutin C, Berthault P, Brotin T . A sensitive zinc-activated 129Xe MRI probe. Angew Chem Int Ed Engl. 2012; 51(17):4100-3. DOI: 10.1002/anie.201109194. View

17.

Murphy E, Steenbergen C, LEVY L, Gabel S, London R . Measurement of cytosolic free calcium in perfused rat heart using TF-BAPTA. Am J Physiol. 1994; 266(5 Pt 1):C1323-9. DOI: 10.1152/ajpcell.1994.266.5.C1323. View

18.

Carter K, Young A, Palmer A . Fluorescent sensors for measuring metal ions in living systems. Chem Rev. 2014; 114(8):4564-601. PMC: 4096685. DOI: 10.1021/cr400546e. View

19.

Taylor K, Jin A, Lin W . Surfactant-assisted synthesis of nanoscale gadolinium metal-organic frameworks for potential multimodal imaging. Angew Chem Int Ed Engl. 2008; 47(40):7722-5. DOI: 10.1002/anie.200802911. View

20.

Mbatia H, Burdette S . Photochemical tools for studying metal ion signaling and homeostasis. Biochemistry. 2012; 51(37):7212-24. DOI: 10.1021/bi3001769. View