Fluorine-19 Magnetic Resonance Spectroscopy

The fluorine chemical shifts of mono-, di-, tri- and tetrahalogenbenzenium ions and their analogues are presented in Tables 19 and 20. There is also evidence available for 2- and 3-fluoro-4-hydroxy- and 4-methoxybenzenium ions as well 

The down-field shift of F signals when protonation of benzene derivatives leads to benzenium ions are usually as follows (ppm) 

33 With respect to C Fs- To pass over to tl 0 scale one should use the relationship 5c + 162.9 

As to the difTerences between perhalogenated benzenium ions and perhalobenzenes corresponding to the formal removal of the cation from the Cj atoms of these ions, Iheir fluorine chemical shifts vary within the ranges (ppm)  

Interestingly, the CF signals of the ions in question are shifted relative to those of the parent perhalocyclohexa-1,4-dienes by 12-19 ppm to the high field. The authors believe the unexpected up-field shift to be due to a specific change in the van der Waals component of the chemical shift for CF upon formation of the ion. 

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W.L. Strauss, A.S. Unis, C. Cowan, G. Dawson, S.R. Dager, Fluorine magnetic resonance spectroscopy measurement of brain fluvoxamine and fluoxetine in pediatric patients treated for pervasive developmental disorders. Am. J. Psychiatry 159 (2002) 755-760. 

N.R. Bolo, Y. Mode, J.P. Macher, Long-term sequestration of fluorinated compounds in tissues after fluvoxamine or fluoxetine treatment A fluorine magnetic resonance spectroscopy study in vivo, MAGMA 16 (2004) 268-276. 

P. Jynge, T. Skjetne, I. Gribbestad, C.H. Kleinbloesem, H.F.W. Hoogkamer, O. Antonsen, J. Krane, O.E. Bakoy, K.M. Furuheim, O.G. Nilsen, In vivo tissue pharmacokinetics by fluorine magnetic-resonance spectroscopy—a study of liver and muscle disposition of fleroxacin in humans, Clin. Pharmacol. Then 48 (1990) 481-489. 

Source Reprinted by permission from Macmillan Publishers Ltd from Boh, N. R., Hode, Y., Nedelec, j. F., et al. Brain pharmacokinetics and tissue distribution in vivo of fluvoxamine and fluoxetine by fluorine magnetic resonance spectroscopy. Neuropsychopharmacology (2000) 23, 428-438.)... 

Bovey, F A, Jelmski, L, Mirau, P A Nuclear Magnetic Resonance Spectroscopy, 2nd ed, Acadermc Press New York, 1988 Proton and Fluorine Nuclear Magnetic Resonance Spectral Data, Vanan Instruments/Japan Halon Tokyo, 1988... 

J. W. Emsley, j. Feeney and L. H. Sutcliffe, High Resolution Nuclear Magnetic Resonance Spectroscopy, Vols. 1 and 2, Pergamon Press, Oxford, 1966, Chap. 11, Fluorine-19, pp. 871-968. 

Fluorine compounds-Spectra. 2. Nuclear magnetic resonance spectroscopy. I. Title. QD412.F1D65 2009 547. 02—dc22... 

Y.L. Chung, H. Troy, I.R. Judson, R. Leek, M.O. Leach, M. Stubbs, A.L. Harris, J.R. Griffiths, Noninvasive measurements of capecitabine metabolism in bladder tumors overexpressing thymidine phosphorylase by fluorine-19 magnetic resonance spectroscopy, Clin. Cancer Res. 10 (2004) 3863-3870. 

T. Frenzel, S. Koszler, H. Bauer, U. Niedballa, H.J. Weinmann, Noninvasive in vivo pH measurement using a fluorinated pH probe and fluorine-19 magnetic resonance spectroscopy. Invest. Radiol. 29 (1994) S220-222. 

B.A. Berkowitz, J.J.H. Ackerman, Proton decoupled fluorine nuclear-magnetic-resonance spectroscopy in situ, Biophys. J. 51 (1987) 681-685. 

B.M. Seddon, R.J. Maxwell, D.J. Floness, R. Grimshaw, F. Raynaud, G.M. Tozer, P. Workman, Validation of the fluorinated 2-nitroimidazole SR-4554 as a noninvasive hypoxia marker detected by magnetic resonance spectroscopy, Clin. Cancer Res. 

E. O. Aboagye, R.J. Maxwell, M.R. Florsman, A.D. Lewis, P. Workman, M. Tracy, J.R. Griffiths, The relationship between tumour oxygenation determined by oxygen electrode measurements and magnetic resonance spectroscopy of the fluorinated 2-nitroimidazole SR-4554, Br. J. Cancer 77 (1998) 65-70. 

Subjects LCSH Fluorine compounds-Spectra. Nuclear magnetic resonance spectroscopy. 

Emsley, J. W., and Phillips, L. (1971). Fluorine chemical shifts. In J. W. Emsley, J. Feeney, and L. H. Sutcliffe, Eds., Progress in Nuclear Magnetic Resonance Spectroscopy, Vol. 7. Oxford Pergamon Press. 

Nuclear magnetic resonance spectroscopy has emerged as the most powerful tool for elucidating the molecular structures of cyclophos-phazene derivatives in solution. Proton NMR spectroscopy has been widely used because of its easy accessibility. The recent development of sophisticated instrumental facilities and the application of broadband proton decoupling have greatly improved the quality and usefulness of the 31P spectra (252) of cyclophosphazenes, and it is likely that this technique will become increasingly popular in the future. Fluorine NMR studies are useful for deducing the structures of fluorocyclophosphazenes, and the potential of this technique has been demonstrated in recent years (209, 210, 213, 307, 308, 343). 

R. Fields Fluorine-19 Nuclear Magnetic Resonance Spectroscopy, pp. 99-304 (513), esp. pp. 255 -286, Transition metal complexes of fluorinated molecules. 

Wray. V. Fluorine-19 Nuclear Magnetic Resonance Spectroscopy. (Ann. Rep. NMR Spectroscopy, Vol. 14) London Academic Press 1983... 

Source Reprinted with permission from Malet-Martino, M., Cilard, V., Desmoulin, F., and Martino, R. Fluorine nuclear magnetic resonance spectroscopy of human biofluids in the field of metabolic studies of anticancer and antifungal fluoropyrimidine drugs, Clin. Chim. Acta (2006) 366, 61-73. Copyright (2006) Elsevier.)... 

Gerig, J. T. (1994) Fluorine NMR of proteins. Progress in Nuclear Magnetic Resonance Spectroscopy, 26, 293-370. 

Study of Metabolism of Fluorine-containing Drugs Using In Vivo Magnetic Resonance Spectroscopy... 

Source Schneider E, Bolo NR, Frederick B et ai, Magnetic resonance spectroscopy for measuring the biodistribution and in situ in vivo pharmacokinetics of fluorinated compounds validation using an investigation of liver and heart disposition of tecastemizole, J. Clin. Pharm. Ther. (2006) 31, 261-273. Copyright (2006) John Wiley Sons. Reprinted with permission.)... 

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