Relaxivity enhancement of low molecular weight nitroxide stable free radicals: Importance of structure and medium

The longitudinal relaxivities of seven water‐soluble nitroxide derivatives ot low‐molecular weight have been measured at 5°C and 37°C in water and in serum between 0.01 and 200 MHz. The nuclear magnetic relaxation dispersion (NMRD) profiles show a clear relationship between the relaxivity observed in serum and the relative balance of the hydrophobichydrophilic character of the paramagnetic molecules. From the data analysis, contributions arising from a population of nitroxides characterized by reduced mobility can be extracted. The values of the correlation times are consistent with a system involving nitroxides adsorbed at the surface of albumin and magnetically interacting with the protons of hydrogen bonded water molecules.

[1]  R. Brasch,et al.  Nitroxyl spin label contrast enhancers for magnetic resonance imaging. Studies of acute toxicity and mutagenesis. , 1984, Investigative radiology.

[2]  G. Sosnovsky A critical evaluation of the present status of toxicity of aminoxyl radicals. , 1992, Journal of pharmaceutical sciences.

[3]  M. Sentjurc,et al.  Hypoxia‐sensitive NMR contrast agents , 1986, Magnetic resonance in medicine.

[4]  Sture Forsén,et al.  Protein hydration from water oxygen-17 magnetic relaxation , 1981 .

[5]  M. Abou‐Donia,et al.  Synthesis of a useful spin labeled probe, 1-oxyl-4-carboxyl-2,2,6,6-tetramethylpiperidine , 1976 .

[6]  Nicolaas Bloembergen,et al.  Proton Relaxation Times in Paramagnetic Solutions , 1957 .

[7]  David J. Lurie,et al.  Proton-electron double magnetic resonance imaging of free radical solutions , 1988 .

[8]  J. Berliner,et al.  Magnetic resonance imaging of biological specimens by electron paramagnetic resonance of nitroxide spin labels. , 1985, Science.

[9]  S. H. Koenig,et al.  Effects of nitroxides on the magnetic field and temperature dependence of 1/T1 of solvent water protons , 1987, Magnetic resonance in medicine.

[10]  S. H. Koenig,et al.  Interactions of nitroxides with plasma and blood: Effect on 1/T1 of water protons , 1990, Magnetic resonance in medicine.

[11]  Harold M. Swartz,et al.  Use of nitroxides to measure redox metabolism in cells and tissues , 1987 .

[12]  R D Williams,et al.  Work in progress: nuclear magnetic resonance study of a paramagnetic nitroxide contrast agent for enhancement of renal structures in experimental animals. , 1983, Radiology.

[13]  Martin Karplus,et al.  SOLVATION. A MOLECULAR DYNAMICS STUDY OF A DIPEPTIDE IN WATER. , 1979 .

[14]  D. Grucker In vivo detection of injected free radicals by overhauser effect imaging , 1990, Magnetic resonance in medicine.

[15]  J. Freed Dynamic effects of pair correlation functions on spin relaxation by translational diffusion in liquids. II. Finite jumps and independent T1 processes , 1978 .

[16]  R. Muller,et al.  Titration of nitroxide free radicals by nuclear magnetic relaxometry , 1990 .

[17]  M. Montgomery,et al.  Determination of serum morphine by the spin-label antibody technique. , 1974, Drug metabolism and disposition: the biological fate of chemicals.

[18]  H. Maeda,et al.  Facile synthesis of monoaza crown ethers , 1981 .

[19]  R. Bryant,et al.  Nitroxide radical induced solvent proton relaxation: Measurement of localized translational diffusion , 1984 .

[20]  I. Bertini,et al.  The electron-nucleus dipolar coupling in slow rotating systems. 2. The effect of g anisotropy and hyperfine coupling when S = 12 and I = 32 , 1985 .

[21]  G. Patey,et al.  The relative motion of ions in solution. I. Microdynamical models and intermolecular dipolar spin relaxation , 1984 .

[22]  I. Solomon Relaxation Processes in a System of Two Spins , 1955 .