Analyzing single-bond experiments: influence of the shape of the energy landscape and universal law between the width, depth, and force spectrum of the bond.

Experimentalists who measure the rupture force of a single molecular bond usually pull on that bond at a constant speed, keeping the loading rate r=df/dt constant. The challenge is to extract the energy landscape of the interaction between the two molecules involved from the experimental rupture force distribution under several loading rates. This analysis requires the use of a model for the shape of this energy landscape. Several barriers can compose the landscape, though molecular bonds with a single barrier are often observed. The Bell model is commonly used for the analysis of rupture force measurements with bonds displaying a single barrier. It provides an analytical expression of the most likely rupture force which makes it very simple to use. However, in principle, it can only be applied to landscapes with extrema whose positions do not vary under force. Here, we evaluate the general relevance of the Bell model by comparing it with another analytical model for which the landscape is harmonic in the vicinity of its extrema. Similar shapes of force distributions are obtained with both models, making it difficult to confirm the validity of the Bell model for a given set of experimental data. Nevertheless, we show that the analysis of rupture force experiments on such harmonic landscapes with the Bell model provides excellent results in most cases. However, numerical computation of the distributions of the rupture forces on piecewise-linear energy landscapes indicates that the blind use of any model such as the Bell model may be risky, since there often exist several landscapes compatible with a given set of experimental data. Finally, we derive a universal relation between the range and energy of the bond and the force spectrum. This relation does not depend on the shape of the energy landscape and can thus be used to characterize unambiguously any one-barrier landscape from experiments. All the results are illustrated with the streptavidin-biotin bond.