The reaction of lanthanide ions with n-doxyl stearic acid ( nDS) spin labels ( n=5,7,12,16) was investigated by the electron spin resonance technique in aqueous solution. Among the lanthanides, the Gd 3+, Tb 3+, Tm 3+ and Ce 3+ ions strongly quenched the ESR signal of spin labels, but the effects of La 3+, Eu 3+ and Lu 3+ are very weak. The quenching effects are featured by: (1) the dependence on the concentration of lanthanide ions; (2) no obvious changes of the ESR line shape in the presence of lanthanide ions; (3) the quenching constant decreases in the order: Gd 3+ > Tb 3+ > Tm 3+ > Ce 3+; (4) the quenching effects of lanthanide ions are found to strikingly correlate with their magnetic properties. These findings indicate that the interaction of lanthanide ions with nitroxide oxygen leading to the reduction of ESR signal amplitude is dominated by their magnetic characteristics rather than the coordination effect. By labeling erythrocyte membrane with nDS, n=5,7,12,16 at different depths, we studied the diffusion of Gd 3+ into the lipid-bilayer of erythrocyte membrane by monitoring the reduction processes of the ESR signals of nitroxide spin labels located at different depths of membrane lipid-bilayer after addition of Gd 3+. These results revealed that the Gd 3+ ions can penetrate into the lipid-bilayer, though the entry rate is slow. It was shown that the Gd 3+ ions bind to the membrane and enhance the permeability of extracellular ascorbate into erythrocyte membrane. The transport mechanism of Gd 3+ ions through the lipid-bilayer might be involved in the Gd 3+ cation-induced pore formation in the surface of membrane.
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