No abstract

A strategy for the fast analysis of ion transfer/facilitated ion transfer toward a tiny (femtoliter) water-in-oil droplet has been established. This scenario is embodied by the fusion of a w/o microdroplet at the micro liquid/liquid (L/L) interface, with the use of Fourier transform fast-scan cyclic voltammetry (FT-FSCV) to express the apparent half-wave potentials of anions or cations encapsulated inside the w/o microdroplet. First, the half-wave potential is in strict accordance with the transfer Gibbs free energy of either cations or anions. Second, the half-wave potential has been found to be positively proportional to the logarithmic concentration of ions, shedding thermodynamic insight into ion transfer. Third, as an instance of multivalent biopolymers, the transfer of protamine inside the single w/o microdroplet has been investigated. Obvious discrepancies in the behaviors of the fusion impacts at different pH, as well as in the absence and presence of the cationic surfactant DNNS–, are revealed. The internal mechanism of protamine transfer has been thoroughly investigated. This work proposes a strategy to sensitively and quickly determine the transfer Gibbs energy and the concentration of ions encapsulated in a single microdroplet, and it provides the possibility of analyzing the interfacial transfer properties of trace biomacromolecules inside an aqueous micro- or nanoscale droplet.

A new subtype of nano-impacts by emulsion droplets via reorganization of the electric double layer (EDL) at the liquid/ liquid interface (LLI) is reported. This subtype shows anodic, bipolar, and cathodic transient currents with a potential of zero charge (PZC) dependence, revealing the non-faradic characteristic of single fusion impacts. In addition, the absolute integrated mean charge is proportional to the Galvani potential at the ITIES, indicating that the EDL at the LLI may obey the discrete Helmholtz model. The exact PZC point is interpolated from the fitting curve, and the droplet size distribution is estimated from the integrated charge distribution. Moreover, the different values of E pzc between single fusion impacts of MgCl 2 droplets and pure water droplets is due to the specific absorption between Mg 2+ and antagonistic anion in the organic phase. The influence of the concentration of the supporting electrolyte is also investigated. The above work gives physicochemical insights into the EDL at the micropipette-supported LLI and provides potential application to measure micro/nanoscale heterogeneous media without catalytic, reactive, or charge-transfer activity via impact experiments at LLI.