Environmentally sensitive paramagnetic and diamagnetic contrast agents for nuclear magnetic resonance imaging and Spectroscopy

Current Topics in Medicinal Chemistry

Volumn 11, Issue 1, 2011, Pages 115-130

  Pacheco Torres, Jesus ^a   Calle, Daniel ^a   Lizarbe, Blanca ^a   Negri, Viviana ^b   Ubide, Carmen ^b   Fayos, Rosa ^a   Larrubia, Pilar López ^a   Ballesteros, Paloma ^b   Cerdan, Sebastian ^a  

^a INSTITUTO DE INVESTIGACIONES BIOMÉDICAS ALBERTO SOLS   (Spain)

^b UNIVERSIDAD NACIONAL DE EDUCACIÓN A DISTANCIA   (Spain)

Author keywords

13C Hyperpolarized molecules; Contrast Mechanisms; Diamagnetic Contrast Agents; Magnetic Resonance Imaging; Magnetic Resonance Spectroscopy; Molecular Imaging; Paramagnetic Contrast Agents; Tissue Microenvironment

Indexed keywords

BARBITURIC ACID; CALCIUM ION; CARBON 13; CHELATING AGENT; CONTRAST MEDIUM; EUROPIUM; GADOLINIUM; GLUCOSE; IMIDAZOLE DERIVATIVE; IRON; LACTIC ACID; MANGANESE; PENTETIC ACID; WATER;

ARTICLE; CELL PH; CONTRAST ENHANCEMENT; DIFFUSION COEFFICIENT; ENZYME ACTIVITY; GENE EXPRESSION; HYPERPOLARIZATION; MICROENVIRONMENT; MOLECULAR IMAGING; MOLECULAR PROBE; NUCLEAR MAGNETIC RESONANCE IMAGING; OXYGEN TENSION; PH MEASUREMENT; PHYSICAL CHEMISTRY; PROTON TRANSPORT; SENSOR; SPECTROSCOPY;

ANIMALS; CONTRAST MEDIA; DIFFUSION; HUMANS; HYDROGEN-ION CONCENTRATION; MAGNETIC RESONANCE IMAGING; MAGNETIC RESONANCE SPECTROSCOPY; OXYGEN;

EID: 78649959879     PISSN: 15680266     EISSN: None     Source Type: Journal    
DOI: 10.2174/156802611793611904     Document Type: Article

References (132)

1. Elaut, G.; Henkens, T.; Papeleu, P.; Snykers, S.; Vinken, M.; Vanhaecke, T.; Rogiers, V. Molecular mechanisms underlying the dedifferentiation process of isolated hepatocytes and their cultures. Curr. Drug Metab., 2006, 7, 629-660.
2. Xiang, S.; Pan, W.; Kastin, A. J. Strategies to create a regenerating environment for the injured spinal cord. Curr. Pharm. Biotechnol., 2005, 11, 1267-1277.
3. Munoz-Chapuli, R.; Quesada, A. R.; Angel Medina, M. Angiogenesis and signal transduction in endothelial cells. Cell. Mol. Life Sci., 2004, 61, 2224-2243.
4. Cairns, R. A.; Khokha, R.; Hill, R. P. Molecular mechanisms of tumor invasion and metastasis: an integrated view. Curr. Mol. Med., 2003, 3, 659-6571.
5. Pathania, M.; Yan, L. D.; Bordey, A. A symphony of signals conducts early and late stages of adult neurogenesis. Neuropharmacology, 2010, 58, 865-876.
6. Haddad, J. J. Oxygen-sensing mechanisms and the regulation of redox-responsive transcription factors in development and pathophysiology. Respir. Res., 2002, 3, 26.
7. Taoufik, E.; Probert, L. Ischemic neuronal damage. Curr. Pharm. Biotechnol., 2008, 14, 3565-3573.
8. Gatenby, R. A.; Gillies, R. J. A microenvironmental model of carcinogenesis. Nat. Rev. Cancer, 2008, 8, 56-61.
9. Joyce, J. A.; Pollard, J. W. Microenvironmental regulation of metastasis. Nat. Rev. Cancer, 2009, 9, 239-252.
10. Meads, M. B.; Gatenby, R. A.; Dalton, W. S. Environmentmediated drug resistance: a major contributor to minimal residual disease. Nat. Rev. Cancer, 2009, 9, 665-674.
11. Sloane, B. F.; Gillies, R. J.; Mohla, S.; Sogn, J. A.; Menkens, A. E.; Sullivan, D. C. I2 imaging: cancer biology and the tumor microenvironment. Cancer Res., 2006, 66, 11097-11099.
12. Jordan, B. F.; Runquist, M.; Raghunand, N.; Baker, A.; Williams, R.; Kirkpatrick, L.; Powis, G.; Gillies, R. J. Dynamic contrastenhanced and diffusion MRI show rapid and dramatic changes in tumor microenvironment in response to inhibition of HIF-1alpha using PX-478. Neoplasia, 2005, 7, 475-485.
13. Gillies, R. J.; Raghunand, N.; Karczmar, G. S.; Bhujwalla, Z. M. MRI of the tumor microenvironment. J. Magn. Reson. Imaging, 2002, 16, 430-450.
14. De Leon-Rodriguez, L. M.; Lubag, A. J.; Malloy, C. R.; Martinez, G. V.; Gillies, R. J.; Sherry, A. D. Responsive MRI agents for sensing metabolism in vivo. Acc. Chem. Res., 2009, 42, 948-957.
15. Aime, S.; Castelli, D. D.; Crich, S. G.; Gianolio, E.; Terreno, E. Pushing the sensitivity envelope of lanthanide-based magnetic resonance imaging (MRI) contrast agents for molecular imaging applications. Acc. Chem. Res., 2009, 42, 822-831.
16. Sherry, A. D.; Woods, M. Chemical exchange saturation transfer contrast agents for magnetic resonance imaging. Annu. Rev. Biomed. Eng., 2008, 10, 391-411.
17. Raghunand, N.; Jagadish, B.; Trouard, T. P.; Galons, J. P.; Gillies, R. J.; Mash, E. A. Redox-sensitive contrast agents for MRI based on reversible binding of thiols to serum albumin. Magn. Reson. Med., 2006, 55, 1272-1280.
18. Caravan, P. Strategies for increasing the sensitivity of gadolinium based MRI contrast agents. Chem. Soc. Rev., 2006, 35, 512-523.
19. Ronald, J. A.; Chen, J. W.; Chen, Y.; Hamilton, A. M.; Rodriguez, E.; Reynolds, F.; Hegele, R. A.; Rogers, K. A.; Querol, M.; Bogdanov, A.; Weissleder, R.; Rutt, B. K. Enzyme-sensitive magnetic resonance imaging targeting myeloperoxidase identifies active inflammation in experimental rabbit atherosclerotic plaques. Circulation, 2009, 120, 592-599.
20. Querol, M.; Bogdanov, A. Jr. Environment-sensitive and enzymesensitive MR contrast agents. Handb. Exp. Pharmacol., 2008, 37-57.
21. Perez-Mayoral, E.; Negri, V.; Soler-Padros, J.; Cerdan, S.; Ballesteros, P. Chemistry of paramagnetic and diamagnetic contrast agents for Magnetic Resonance Imaging and Spectroscopy pH responsive contrast agents. Eur. J. Radiol., 2008, 67, 453-458.
22. Gillies, R. J. Nuclear magnetic resonance and its applications to physiological problems. Annu. Rev. Physiol., 1992, 54, 733-748.
23. Skoch, A.; Jiru, F.; Bunke, J. Spectroscopic imaging: basic principles. Eur. J. Radiol., 2008, 67, 230-239.
24. Constable, E. C. Coordination Chemistry of Macrocycles Compounds. Oxford University Press: New York, 1999.
25. Pérez-Mayoral, E.; Soler-Padrós, J.; Negri, V.; Cerdán, S.; Ballesteros, P. Synthetic Approaches to Heterocyclic Ligands for Gd- Based MRI Contrast Agents. Molecules, 2007, 12, 1771-1795.
26. Ballesteros, P. In: Flexible tetraazamacrocyles as contrast agents for Magnetic Resonance Imaging. Research Signpost, XXX, Ed. 2005; Vol. 1, pp 512-532.
27. Vincent, J.; Desreux, J.-F. Synthesis of MRI contrast agents II: Macrocyclic ligands. In The Chemistry of Contrast Agents in Medical Magnetic Resonance Imaging, Merbach, A. E. a. T., E., Ed. John Wiley and Sons: Chichester, 2002, pp. 157-192.
28. Morawski, A. M.; Lanza, G. A.; Wickline, S. A. Targeted contrast agents for magnetic resonance imaging and ultrasound. Curr. Opin. Biotechnol., 2005, 16, 89-92.
29. Aime, S.; Botta, M.; Fasano, M.; Terreno, E. Protein-Bound Metal Chelates In The chemistry of Contrast Agents for Medical Magnetic Resonance Imaging, Merbach, A. E. a. T., E., Ed. John Wiley and Sons: Chichester, 2002.
30. Laurent, S.; Boutry, S.; Mahieu, I.; Vander Elst, L.; Muller, R. N. Iron oxide based MR contrast agents: from chemistry to cell labeling. Curr. Med. Chem., 2009, 16, 4712-4727.
31. Petri-Fink, A.; Hofmann, H. Superparamagnetic iron oxide nanoparticles (SPIONs): from synthesis to in vivo studies--a summary of the synthesis, characterization, in vitro, and in vivo investigations of SPIONs with particular focus on surface and colloidal properties. IEEE Trans. Nanobiosci., 2007, 6, 289-297.
32. Aime, S.; Castelli, D. D.; Crich, S. G.; Gianolio, E.; Terreno, E. Pushing the sensitivity envelope of lanthanide-based magnetic resonance imaging (MRI) contrast agents for molecular imaging applications. Acc. Chem. Res., 2009, 42, 822-831.
33. Aime, S.; Castelli, D. D.; Terreno, E. Chapter 10 - Lanthanideloaded paramagnetic liposomes as switchable magnetically oriented nanovesicles. Methods Enzymol., 2009, 464, 193-210.
34. Burdinski, D.; Pikkemaat, J. A.; Emrullahoglu, M.; Costantini, F.; Verboom, W.; Langereis, S.; Grull, H.; Huskens, J. Targeted Lipo- CEST Contrast Agents for Magnetic Resonance Imaging: Alignment of Aspherical Liposomes on a Capillary Surface. Angew. Chem. Int. Ed. Engl., 2010, 49(12), 2227-2229.
35. Merbach, A. E.; Tóth, E. The Chemistry of Contrast Agents in Medical Resonance Imaging. Wiley: Chichester, 2001.
36. Krause, W. Contrast Agents I: Magnetic Resonance Imaging. Springer: Berlin, 2002, Vol. 221.
37. Caravan, P.; Ellison, J. J.; McMurry, T. J.; Lauffer, R. B. Gadolinium(III) Chelates as MRI Contrast Agents: Structure, Dynamics, and Applications. Chem. Rev., 1999, 99, 2293-2352.
38. Aime, S.; Barge, A.; Gianolio, E.; Pagliarin, R.; Silengo, L.; Tei, L. High relaxivity contrast agents for MRI and molecular imaging. Ernst Schering Res. Found. Workshop, 2005, 99-121.
39. Aime, S.; Barge, A.; Cabella, C.; Crich, S. G.; Gianolio, E. Targeting cells with MR imaging probes based on paramagnetic Gd(III) chelates. Curr. Pharm. Biotechnol., 2004, 5, 509-518.
40. Cai, W.; Chen, X. Nanoplatforms for targeted molecular imaging in living subjects. Small, 2007, 3, 1840-1854.
41. Thorek, D. L.; Chen, A. K.; Czupryna, J.; Tsourkas, A. Superparamagnetic iron oxide nanoparticle probes for molecular imaging. Ann. Biomed. Eng., 2006, 34, 23-38.
42. Cintra, E. R.; Ferreira, F. S.; Santos Junior, J. L.; Campello, J. C.; Socolovsky, L. M.; Lima, E. M.; Bakuzis, A. F. Nanoparticle agglomerates in magnetoliposomes. Nanotechnology, 2009, 20, 45103.
43. Toth, E.; Helm, L.; Merbach, A. E. Relaxivity of Gadolinium (III) complexes: Theory and mechanism. In The Chemistry of Contrast Agents in Medical Magnetic Resonance Imaging, Merbach, A. E. a. T., E., Ed. John Wiley and Sons: Chichester, 2002, pp 45-120.
44. Idee, J. M.; Port, M.; Robic, C.; Medina, C.; Sabatou, M.; Corot, C. Role of thermodynamic and kinetic parameters in gadolinium chelate stability. J. Magn. Reson. Imaging, 2009, 30, 1249-1258.
45. Sherry, A. D.; Caravan, P.; Lenkinski, R. E. Primer on gadolinium chemistry. J. Magn. Reson. Imaging, 2009, 30, 1240-1248.
46. Canavese, C.; Mereu, M. C.; Aime, S.; Lazzarich, E.; Fenoglio, R.; Quaglia, M.; Stratta, P. Gadolinium-associated nephrogenic systemic fibrosis: the need for nephrologists' awareness. J. Nephrol., 2008, 21, 324-236.
47. Stratta, P.; Canavese, C.; Aime, S. Gadolinium-enhanced magnetic resonance imaging, renal failure and nephrogenic systemic fibrosis/ nephrogenic fibrosing dermopathy. Curr. Med. Chem., 2008, 15, 1229-1235.
48. Lauffer, R. B. Paramagnetic metal complexes as water proton relaxation agents for NMR imaging: theory and design. Chem. Rev., 1987, 87, 901-927.
49. Garcia-Martín, M. L.; Ballesteros, P.; Cerdan, S. The metabolism of water in cells and tissues as detected by Magnetic Resonance methods. Prog. Nucl. Mag. Res. Spec., 1999, 39, 41-77.
50. Henkelman, R. M.; Stanisz, G. J.; Graham, S. J. Magnetization transfer in MRI: a review. NMR Biomed., 2001, 14, 57-64.
51. Forsén, S.; Hoffman, R. A. Study of moderately rapid chemical exchange reactions by means of nuclear magnetic resonance double resonance. J. Che. Phys., 1963, 39, 2892-2901.
52. Nitz, W. R.; Reimer, P. Contrast mechanisms in MR imaging. Eur. Radiol., 1999, 9, 1032-1046.
53. Zhou, J.; Zijl, P. C. M. v. Chemical exchange saturation transfer imaging and spectroscopy. Prog. Nucl. Mag. Res. Spec., 2006, 48, 109-136.
54. Zhou, J.; Lal, B.; Wilson, D. A.; Laterra, J.; van Zijl, P. C. Amide proton transfer (APT) contrast for imaging of brain tumors. Magn. Reson. Med., 2003, 50, 1120-1126.
55. Sun, P. Z.; Zhou, J.; Huang, J.; van Zijl, P. Simplified quantitative description of amide proton transfer (APT) imaging during acute ischemia. Magn. Reson. Med., 2007, 57, 405-410.
56. Zhou, J.; Wilson, D. A.; Sun, P. Z.; Klaus, J. A.; Van Zijl, P. C. Quantitative description of proton exchange processes between water and endogenous and exogenous agents for WEX, CEST, and APT experiments. Magn. Reson. Med., 2004, 51, 945-952.
57. Zhou, J.; Payen, J. F.; Wilson, D. A.; Traytsman, R. J.; van Zijl, P. C. Using the amide proton signals of intracellular proteins and peptide to detect pH effects in MRI. Nat. Med., 2003, 9, 1085-1090.
58. Ward, K. M.; Balaban, R. S. Determination of pH using water protons and chemical exchange dependent saturation transfer (CEST). Magn. Reson. Med., 2000, 44, 799-802.
59. Ward, K. M.; Aletras, A. H.; Balaban, R. S. A new class of contrast agents for MRI based on proton chemical exchange dependent saturation transfer (CEST). J. Magn. Reson., 2000, 143, 79-87.
60. Le Bihan, D. Looking into the functional architecture of the brain with diffusion MRI. Nature, 2003, 4, 469-480.
61. Le Bihan, D.; Manguin, J.-F.; Poupon, C.; Clark, C. A.; Pappatta, S.; Molko, N.; Chabriat, H. Diffusion Tensor Imaging: Concepts and Applications. J. Mag. Res. Imag, 13, 534-546.
62. Nucifora, P. G.; Verma, R.; Lee, S. K.; Melhem, E. R. Diffusiontensor MR imaging and tractography: exploring brain microstructure and connectivity. Radiology, 2007, 245, 367-384.
63. Negri, V.; Cerpa, A.; Lopez-Larrubia, P.; Nieto-Charques, L.; Cerdan, S.; Ballesteros, P. Nanotubular paramagnetic probes as contrast agents for magnetic resonance imaging based on the diffusion tensor. Angew Chem. Int. Ed. Engl., 2010, 49, 1813-1815.
64. Gillies, R. J.; Raghunand, N.; Garcia-Martin, M. L.; Gatenby, R. A. pH imaging. A review of pH measurement methods and applications in cancers. IEEE Eng. Med. Biol. Mag., 2004, 23, 57-64.
65. Gillies, R. J.; Ugurbil, K.; den Hollander, J. A.; Shulman, R. G. 31P NMR studies of intracellular pH and phosphate metabolism during cell division cycle of Saccharomyces cerevisiae. Proc. Natl. Acad. Sci. USA, 1981, 78, 2125-2129.
66. Gadian, D. G.; Radda, G. K. NMR studies of tissue metabolism. Annu. Rev. Biochem., 1981, 50, 69-83.
67. DeFronzo, M.; Gillies, R. J. Characterization of methylphosphonate as a 31P NMR pH indicator. J. Biol. Chem., 1987, 262, 11032-11037.
68. Bore, P. J.; Chan, L.; Gadian, D. G.; Radda, G. K.; Ross, B. D.; Styles, P.; Taylor, D. J. Noninvasive pHi measurements of human tissue using 31P-NMR. Kroc Found. Ser., 1981, 15, 527-535.
69. Perez-Mayoral, E.; Negri, V.; Soler-Padros, J.; Cerdan, S.; Ballesteros, P. Chemistry of paramagnetic and diamagnetic contrast agents for Magnetic Resonance Imaging and Spectroscopy pH responsive contrast agents. Eur. J. Radiol., 2008, 67, 453-458.
70. Gil, S.; Zaderenzo, P.; Cruz, F.; Cerdan, S.; Ballesteros, P. Imidazol- 1-ylalkanoic acids as extrinsic 1H NMR probes for the determination of intracellular pH, extracellular pH and cell volume. Bioorg. Med. Chem., 1994, 2, 305-314.
71. Ljungkvist, A. S.; Bussink, J.; Kaanders, J. H.; van der Kogel, A. J. Dynamics of tumor hypoxia measured with bioreductive hypoxic cell markers. Radiat. Res., 2007, 167, 127-145.
72. Padhani, A. R.; Krohn, K. A.; Lewis, J. S.; Alber, M. Imaging oxygenation of human tumours. Eur. Radiol., 2007, 17, 861-872.
73. Chapman, J. D.; Engelhardt, E. L.; Stobbe, C. C.; Schneider, R. F.; Hanks, G. E. Measuring hypoxia and predicting tumor radioresistance with nuclear medicine assays. Radiother. Oncol., 1998, 46, 229-237.
74. Koch, C. J. Measurement of absolute oxygen levels in cells and tissues using oxygen sensors and 2-nitroimidazole EF5. Methods Enzymol., 2002, 352, 3-31.
75. Evans, S. M.; Judy, K. D.; Dunphy, I.; Jenkins, W. T.; Nelson, P. T.; Collins, R.; Wileyto, E. P.; Jenkins, K.; Hahn, S. M.; Stevens, C. W.; Judkins, A. R.; Phillips, P.; Geoerger, B.; Koch, C. J. Comparative measurements of hypoxia in human brain tumors using needle electrodes and EF5 binding. Cancer Res., 2004, 64, 1886-1892.
76. Brezden, C. B.; Horn, L.; McClelland, R. A.; Rauth, A. M. Oxidative stress and 1-methyl-2-nitroimidazole cytotoxicity. Biochem. Pharmacol., 1998, 56, 335-344.
77. Varghese, A. J.; Whitmore, G. F. Properties of 2-hydroxylaminoimidazoles and their implications for the biological effects of 2-nitroimidazoles. Chem. Biol. Interact., 1985, 56, 269-287.
78. Bolton, J. L.; McClelland, R. A. Kinetics and mechanism of the decomposition in aqueous solutions of 2-(hydroxyamino) imidazoles. J. Am. Chem. Soc., 1989, 111, 8172-8181.
79. Seddon, B. M.; Workman, P. The role of functional and molecular imaging in cancer drug discovery and development. Br. J. Radiol., 2003, 76, S128-S138.
80. Ardenkjaer-Larsen, J. H.; Fridlund, B.; Gram, A.; Hansson, G.; Hansson, L.; Lerche, M. H.; Servin, R.; Thaning, M.; Golman, K. Increase in signal-to-noise ratio of > 10, 000 times in liquid-state NMR. Proc. Natl. Acad. Sci. USA, 2003, 100, 10158-10163.
81. Golman, K.; Ardenkjaer-Larsen, J. H.; Petersson, J. S.; Mansson, S.; Leunbach, I. Molecular imaging with endogenous substances. Proc. Natl. Acad. Sci. USA, 2003, 100, 10435-10439.
82. Golman, K.; Zandt, R. I.; Lerche, M.; Pehrson, R.; Ardenkjaer-Larsen, J. H. Metabolic imaging by hyperpolarized 13C magnetic resonance imaging for in vivo tumor diagnosis. Cancer Res., 2006, 66, 10855-10860.
83. Kurhanewicz, J.; Bok, R.; Nelson, S. J.; Vigneron, D. B. Current and potential applications of clinical 13C MR spectroscopy. J. Nucl. Med., 2008, 49, 341-344.
84. Mansson, S.; Johansson, E.; Magnusson, P.; Chai, C. M.; Hansson, G.; Petersson, J. S.; Stahlberg, F.; Golman, K. 13C imaging-a new diagnostic platform. Eur. Radiol., 2006, 16, 57-67.
85. Comment, A.; Rentsch, J.; Kurdzesau, F.; Jannin, S.; Uffmann, K.; van Heeswijk, R. B.; Hautle, P.; Konter, J. A.; van den Brandt, B.; van der Klink, J. J. Producing over 100 ml of highly concentrated hyperpolarized solution by means of dissolution DNP. J. Magn. Reson., 2008, 194, 152-155.
86. Yen, Y. F.; Kohler, S. J.; Chen, A. P.; Tropp, J.; Bok, R.; Wolber, J.; Albers, M. J.; Gram, K. A.; Zierhut, M. L.; Park, I.; Zhang, V.; Hu, S.; Nelson, S. J.; Vigneron, D. B.; Kurhanewicz, J.; Dirven, H. A.; Hurd, R. E. Imaging considerations for in vivo 13C metabolic mapping using hyperpolarized 13C-pyruvate. Magn. Reson Med., 2009, 62, 1-10.
87. Schroeder, M. A.; Atherton, H. J.; Ball, D. R.; Cole, M. A.; Heather, L. C.; Griffin, J. L.; Clarke, K.; Radda, G. K.; Tyler, D. J. Real-time assessment of Krebs cycle metabolism using hyperpolarized 13C magnetic resonance spectroscopy. FASEB J., 2009, 23, 2529-2538.
88. Albers, M. J.; Bok, R.; Chen, A. P.; Cunningham, C. H.; Zierhut, M. L.; Zhang, V. Y.; Kohler, S. J.; Tropp, J.; Hurd, R. E.; Yen, Y. F.; Nelson, S. J.; Vigneron, D. B.; Kurhanewicz, J. Hyperpolarized 13C lactate, pyruvate, and alanine: noninvasive biomarkers for prostate cancer detection and grading. Cancer Res., 2008, 68, 8607-8615.
89. Gallagher, F. A.; Kettunen, M. I.; Day, S. E.; Hu, D. E.; Ardenkjaer-Larsen, J. H.; Zandt, R.; Jensen, P. R.; Karlsson, M.; Golman, K.; Lerche, M. H.; Brindle, K. M. Magnetic resonance imaging of pH in vivo using hyperpolarized 13C-labelled bicarbonate. Nature, 2008, 453, 940-943.
90. Schroeder, M. A.; Swietach, P.; Atherton, H. J.; Gallagher, F. A.; Lee, P.; Radda, G. K.; Clarke, K.; Tyler, D. J. Measuring intracellular pH in the heart using hyperpolarized carbon dioxide and bicarbonate: a 13C and 31P magnetic resonance spectroscopy study. Cardiovasc. Res., 2010, 86(1), 82-91.
91. Bruce, J. I.; Dickins, R. S.; Govenlock, L. J.; Gunnlaugsson, T.; Lopinski, S.; Lowe, M. P.; Parker, D.; Peacock, R. D.; Perry, J. J. B.; Aime, S.; Botta, M. The selectivity of reversible oxy-anion binding in aqueous solution at a chiral europium and terbium center: signaling of carbonate chelation by changes in the form and circular polarization of luminescence emission. J. Am. Chem. Soc., 2000, 122, 9674-9684.
92. Zhang, S.; Wu, K.; Sherry, A. D. A Novel pH-Sensitive MRI Contrast Agent. Angew. Chem. Int. Ed. Engl., 1999, 38, 3192-3194.
93. Garcia-Martin, M. L.; Martinez, G. V.; Raghunand, N.; Sherry, A. D.; Zhang, S.; Gillies, R. J. High resolution pH(e) imaging of rat glioma using pH-dependent relaxivity. Magn. Reson. Med., 2006, 55, 309-315.
94. Raghunand, N.; Howison, C.; Sherry, A. D.; Zhang, S.; Gillies, R. J. Renal and systemic pH imaging by contrast-enhanced MRI. Magn. Reson. Med., 2003, 49, 249-257.
95. Raghunand, N.; Zhang, S.; Sherry, A. D.; Gillies, R. J. In vivo magnetic resonance imaging of tissue pH using a novel pHsensitive contrast agent, GdDOTA-4AmP. Acad. Radiol., 2002, 9 (Suppl 2), S481-483.
96. Aime, S.; Fedeli, F.; Sanino, A.; Terreno, E. A R2/R1 ratiometric procedure for a concentration-independent, pH-responsive, Gd(III)- based MRI agent. J. Am. Chem. Soc., 2006, 128, 11326-11327.
97. Aime, S.; Barge, A.; Botta, M.; Howard, J. A. K.; Kataky, R.; Lowe, M. P.; Moloney, J. M.; Parker, D.; de Sousa, A. S. Dependence of the relaxivity and luminescence of gadolinium and europium amino-acid complexes on hydrogencarbonate and pH. Chem. Commun., 1999, 1047 - 1048.
98. Terreno, E.; Botta, M.; Dastru, W.; Aime, S. Gd-enhanced MR images of substrates other than water. Contrast Media Mol. Imaging, 2006, 1, 101-105.
99. Aime, S.; Barge, A.; Delli Castelli, D.; Fedeli, F.; Mortillaro, A.; Nielsen, F. U.; Terreno, E. Paramagnetic lanthanide(III) complexes as pH-sensitive chemical exchange saturation transfer (CEST) contrast agents for MRI applications. Magn. Reson. Med., 2002, 47, 639-648.
100. Aime, S.; Delli Castelli, D.; Fedeli, F.; Terreno, E. A paramagnetic MRI-CEST agent responsive to lactate concentration. J. Am. Chem. Soc., 2002, 124, 9364-9365.
101. Zhang, S.; Merritt, M.; Woessner, D. E.; Lenkinski, R. E.; Sherry, A. D. PARACEST agents: modulating MRI contrast via water proton exchange. Acc. Chem. Res., 2003, 36, 783-790.
102. Terreno, E.; Stancanello, J.; Longo, D.; Castelli, D. D.; Milone, L.; Sanders, H. M.; Kok, M. B.; Uggeri, F.; Aime, S. Methods for an improved detection of the MRI-CEST effect. Contrast Media Mol. Imaging, 2009, 4, 237-247.
103. Helm, L.; Merbach, A. E. Inorganic and bioinorganic solvent exchange mechanisms. Chem. Rev., 2005, 105, 1923-1959.
104. Trokowski, R.; Zhang, S.; Sherry, A. D. Cyclen-based phenylboronate ligands and their Eu3+ complexes for sensing glucose by MRI. Bioconj. Chem., 2004, 15, 1431-1440.
105. Ren, J.; Trokowski, R.; Zhang, S.; Malloy, C. R.; Sherry, A. D. Imaging the tissue distribution of glucose in livers using a PARACEST sensor. Magn. Reson. Med., 2008, 60, 1047-1055.
106. Chang, Y. T.; Cheng, C. M.; Su, Y. Z.; Lee, W. T.; Hsu, J. S.; Liu, G. C.; Cheng, T. L.; Wang, Y. M. Synthesis and characterization of a new bioactivated paramagnetic gadolinium(III) complex Gd(DOTA-FPG)(H2O) for tracing gene expression. Bioconj. Chem., 2007, 18, 1716-1727.
107. Zhang, S.; Malloy, C. R.; Sherry, A. D. MRI thermometry based on PARACEST agents. J. Am. Chem. Soc., 2005, 127, 17572-17573.
108. Li, A. X.; Wojciechowski, F.; Suchy, M.; Jones, C. K.; Hudson, R. H.; Menon, R. S.; Bartha, R. A sensitive PARACEST contrast agent for temperature MRI: Eu3+-DOTAM-glycine (Gly)- phenylalanine (Phe). Magn. Reson. Med., 2008, 59, 374-381.
109. Gilad, A. A.; Ziv, K.; McMahon, M. T.; van Zijl, P. C.; Neeman, M.; Bulte, J. W. MRI reporter genes. J. Nucl. Med. 2008, 49, 1905-1908.
110. Louie, A. Y.; Huber, M. M.; Ahrens, E. T.; Rothbacher, U.; Moats, R.; Jacobs, R. E.; Fraser, S. E.; Meade, T. J. In vivo visualization of gene expression using magnetic resonance imaging. Nat. Biotechnol. 2000, 18, 321-325.
111. Hanaoka, K.; Kikuchi, K.; Terai, T.; Komatsu, T.; Nagano, T. A Gd3+-based magnetic resonance imaging contrast agent sensitive to beta-galactosidase activity utilizing a receptor-induced magnetization enhancement (RIME) phenomenon. Chemistry, 2008, 14, 987-995.
112. Genove, G.; DeMarco, U.; Xu, H.; Goins, W. F.; Ahrens, E. T. A new transgene reporter for in vivo magnetic resonance imaging. Nat. Med. 2005, 11, 450-454.
113. Goldhawk, D. E.; Lemaire, C.; McCreary, C. R.; McGirr, R.; Dhanvantari, S.; Thompson, R. T.; Figueredo, R.; Koropatnick, J.; Foster, P.; Prato, F. S. Magnetic resonance imaging of cells overexpressing MagA, an endogenous contrast agent for live cell imaging. Mol. Imaging, 2009, 8, 129-139.
114. Zhang, C. Y.; Lu, J.; Tsourkas, A. Iron chelator-based amplification strategy for improved targeting of transferrin receptor with SPIO. Cancer Biol. Ther. 2008, 7, 889-895.
115. Garcia-Martin, M. L.; Herigault, G.; Remy, C.; Farion, R.; Ballesteros, P.; Coles, J. A.; Cerdan, S.; Ziegler, A. Mapping extracellular pH in rat brain gliomas in vivo by 1H magnetic resonance spectroscopic imaging: comparison with maps of metabolites. Cancer Res., 2001, 61, 6524-6531.
116. Provent, P.; Benito, M.; Hiba, B.; Farion, R.; Lopez-Larrubia, P.; Ballesteros, P.; Remy, C.; Segebarth, C.; Cerdan, S.; Coles, J. A.; Garcia-Martin, M. L. Serial in vivo spectroscopic nuclear magnetic resonance imaging of lactate and extracellular pH in rat gliomas shows redistribution of protons away from sites of glycolysis. Cancer Res., 2007, 67, 7638-7645.
117. Varghese, A. J.; Gulyas, S.; Mohindra, J. K. Hypoxia-dependent reduction of 1-(2-nitro-1-imidazolyl)-3-methoxy-2-propanol by Chinese hamster ovary cells and KHT tumor cells in vitro and in vivo. Cancer Res., 1976, 36, 3761-3765.
118. Raleigh, J. A.; Franko, A. J.; Treiber, E. O.; Lunt, J. A.; Allen, P. S. Covalent binding of a fluorinated 2-nitroimidazole to EMT-6 tumors in Balb/C mice: detection by F-19 nuclear magnetic resonance at 2.35 T. Int. J. Radiat. Oncol. Biol. Phys., 1986, 12, 1243-1245.
119. Raleigh, J. A.; Franko, A. J.; Kelly, D. A.; Trimble, L. A.; Allen, P. S. Development of an in vivo 19F magnetic resonance method for measuring oxygen deficiency in tumors. Magn Reson. Med., 1991, 22, 451-466.
120. Aboagye, E. O.; Lewis, A. D.; Tracy, M.; Workman, P. Bioreductive metabolism of the novel fluorinated 2-nitroimidazole hypoxia probe N-(2-hydroxy-3, 3, 3-trifluoropropyl)-2-(2-nitroimidazolyl) acetamide (SR-4554). Biochem. Pharmacol., 1997, 54, 1217-1224.
121. Aboagye, E. O.; Maxwell, R. J.; Kelson, A. B.; Tracy, M.; Lewis, A. D.; Graham, M. A.; Horsman, M. R.; Griffiths, J. R.; Workman, P. Preclinical evaluation of the fluorinated 2-nitroimidazole N-(2- hydroxy-3, 3, 3-trifluoropropyl)-2-(2-nitro-1-imidazolyl) acetamide (SR-4554) as a probe for the measurement of tumor hypoxia. Cancer Res., 1997, 57, 3314-3318.
122. Aboagye, E. O.; Lewis, A. D.; Graham, M. A.; Tracy, M.; Kelson, A. B.; Ryan, K. J.; Workman, P. The pharmacokinetics, bioavailability and biodistribution in mice of a rationally designed 2- nitroimidazole hypoxia probe SR-4554. Anticancer. Drug Des., 1996, 11, 231-242.
123. Seddon, B. M.; Maxwell, R. J.; Honess, D. J.; Grimshaw, R.; Raynaud, F.; Tozer, G. M.; Workman, P. Validation of the fluorinated 2-nitroimidazole SR-4554 as a noninvasive hypoxia marker detected by magnetic resonance spectroscopy. Clin. Cancer Res., 2002, 8, 2323-2335.
124. Seddon, B. M.; Payne, G. S.; Simmons, L.; Ruddle, R.; Grimshaw, R.; Tan, S.; Turner, A.; Raynaud, F.; Halbert, G.; Leach, M. O.; Judson, I.; Workman, P. A phase I study of SR-4554 via intravenous administration for noninvasive investigation of tumor hypoxia by magnetic resonance spectroscopy in patients with malignancy. Clin. Cancer Res., 2003, 9, 5101-5112.
125. Procissi, D.; Claus, F.; Burgman, P.; Koziorowski, J.; Chapman, J. D.; Thakur, S. B.; Matei, C.; Ling, C. C.; Koutcher, J. A. In vivo 19F magnetic resonance spectroscopy and chemical shift imaging of tri-fluoro-nitroimidazole as a potential hypoxia reporter in solid tumors. Clin. Cancer Res., 2007, 13, 3738-3747.
126. Day, S. E.; Kettunen, M. I.; Gallagher, F. A.; Hu, D. E.; Lerche, M.; Wolber, J.; Golman, K.; Ardenkjaer-Larsen, J. H.; Brindle, K. M. Detecting tumor response to treatment using hyperpolarized 13C magnetic resonance imaging and spectroscopy. Nat. Med., 2007, 13, 1382-1387.
127. Schroeder, M. A.; Swietach, P.; Atherton, H. J.; Gallagher, F. A.; Lee, P.; Radda, G. K.; Clarke, K.; Tyler, D. J. Measuring intracellular pH in the heart using hyperpolarized carbon dioxide and bicarbonate: a 13C and 31P magnetic resonance spectroscopy study. Cardiovasc Res., 2010, 86(1), 82-91.
128. Merritt, M. E.; Harrison, C.; Storey, C.; Jeffrey, F. M.; Sherry, A. D.; Malloy, C. R. Hyperpolarized 13C allows a direct measure of flux through a single enzyme-catalyzed step by NMR. Proc. Natl. Acad. Sci. USA, 2007, 104, 19773-19777.
129. Moreno, K. X.; Sabelhaus, S. M.; Merritt, M. E.; Sherry, A. D.; Malloy, C. R. Competition of pyruvate with physiological substra tes for oxidation by the heart: implications for studies with hyperpolarized 1-13CPyruvate. Am. J. Physiol. Heart. Circ. Physiol., 2010, 298(5), H1556-1564.
130. Padhani, A.; Krohn, K.; Lewis, J.; Alber, M. Imaging oxygenation of human tumours. Eur. Radiol., 2007, 17, 861-872.
131. Ljungkvist, A. S. E.; Bussink, J.; Kaanders, J. H. A. M.; van der Kogel, A. Dynamics of tumor hypoxia measured with bioreductive hypoxic cell markers. Radiation Res., 2007, 167, 127-145.
132. Procissi, D.; Claus, F.; Burgman, P.; Koziorowski, J.; Chapman, J. D.; Thakur, S.; Matei, C.; Ling, C. C.; Koutcher, J. In vivo 19F magnetic resonance spectroscopy and chemical shift imaging of trifluoro- nitroimidazole as a potential hypoxia reporter in solid tumors. Clin. Cancer Res., 2007, 13, 3738-3747.