The critical micelle concentration (CMC) of nonionic detergents is defined as the breaking point in the monomer concentration as a function of the total detergent concentration, identified by setting the third derivate of this function to zero. Combined with a mass action model for micelle formation, this definition yields analytic formulae for the concentration ratio of monomers to total detergent at the CMC and the relationship between the CMC and the free energy of micellization g mic. The theoretical breaking point is shown to coincide with the breaking point of the experimental titration curve, if the fluorescence enhancement of 8-anilino-1-naphthalene-sulfonic acid (ANS) or a similar probe dye is used to monitor micelle formation. Application to a series of n-alkyl-β-d-maltosides with the number of carbon atoms in the alkyl chain ranging from 8 to 12 demonstrates the good performance of a molecular thermodynamic model, in which the free energy of micellization is given by g mic = σΦ + g pack + g st. In this model, σ is a fit parameter with the dimension of surface tension, Φ represents the change in area of hydrophobic molecular surfaces in contact with the aqueous phase, and g pack and g st are contributions, respectively, from alkyl chain packing in the micelle interior and steric repulsion of detergent head groups. The analysis of experimental data from different sources shows that varying experimental conditions such as co-solutes in the aqueous phase can be accounted for by adapting only σ, if the co-solutes do not bind to the detergent to an appreciable extent. The model is considered a good compromise between theory and practicability to be applied in the context of in vitro investigations of membrane proteins.
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