The electrochemical collision-blocking technique, equipped with the nanoelectrode of Pt was proposed for determination of the critical micelle concentration (CMC) of non-ionic surfactant TX-100. The approach was found on detection of individual collided nanomicelles in amperometric measurements of the oxidation of K4Fe(CN)6 varying the titrated concentration of TX-100 whereas the formed micelles above the CMC stick on the electrode surface during collision to locally block the flux of electroactive species and further to change the faradaic current. The step-like current transients observed in i-t curves have been demonstrated corresponding to electrochemical collision events of individual TX-100 micelles and micelle aggregates by 3D COMSOL simulations. The logarithm relations between the collision frequency of micelle(s) and the concentration of TX-100 were derived by regression analysis to give the corresponding values of CMC in salt solutions. Further, an 'ideal' CMC of TX-100 without influence of additional salts was estimated to be 0.194 mM using the McDevit-Long theory. The more accurate CMC determined in this work has shown less than the previously reported, mainly due to the detection limit for micelle as low as 0.41 fM. Also, we determined the second CMC of 1.21 mM as the first observation of the collision response of micelle aggregates during TX-100 titration. Owing to its analytical characteristics in single-particle tracking and material insensitivity, the approach we proposed is potentially to be a universal tool for accurate determination of CMC of surfactants, and also for studying the formation of polymer particles at a single-particle level, which is not easily accessible using conventional ensemble measurements.
Keywords: Collision electrochemistry; Critical micelle concentration; Nanoelectrode; Single-particle detection.
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