Several simple models have been proposed to describe the interaction of macromolecules with metal ions in the case of proton relaxation rates measurements in NMR spectroscopy. A new model is proposed to explain the shape of the curves obtained experimentally and to predict new shapes in extreme cases. The originality of the method is that it is possible to detect from plots of experimental data whether the association metal-complexing agent at one site is co-operative or not, which is very important in the determination of the macromolecular structure. © 1969 Academic Press Inc. (London) Ltd.