In this work, the ion-transfer voltammetric detection of the protonated beta-blocker propranolol in artificial saliva is presented. Cyclic voltammetry, differential pulse voltammetry, and differential pulse stripping voltammetry (DPSV) were employed in the detection of the cationic drug based on ion-transfer voltammetry across arrays of microinterfaces between artificial saliva and an organogel phase. It was found that the artificial saliva matrix decreased the available potential window for ion-transfer voltammetry at this liquid|liquid interface but transfer of protonated propranolol was still achieved. The DPSV method employed a preconditioning step as well as a preconcentration step followed by analytical signal generation based on the back-transfer of the drug across the array of microinterfaces. The DPSV peak current response was linear with drug concentration in the artificial saliva matrix over the concentration range of 0.05-1 microM (i(p) = -8.13 (nA microM(-1))(concentration) + 0.07 (nA), R = 0.9929, n = 7), and the calculated detection limit (3s(b)) was 0.02 microM. These results demonstrate that DPSV at arrays of liquid|liquid microinterfaces is a viable analytical approach for pharmaceutical determinations in biomimetic matrixes.

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The electrochemistry of a series of dendrimers was examined at the interface between two immiscible electrolyte solutions (ITIES), enabling study of non-redox-active dendrimers. Different generations of poly(propylenimine) (DAB-AM-n) and poly(amidoamine) (PAMAM) dendrimers were studied. In their protonated states, the dendrimers were transferred across the ITIES, with the electrochemical behavior observed depending on the dendrimer family, the generation number, and the experimental pH. The electrochemistry of the lower generations studied was characterized by well-defined peaks for both dendrimer families and with small peak-peak separations in the case of the PAMAM family. The voltammetry of the higher generations was more complex, showing distorted voltammograms and instability of the interface. The charges of the transferring dendrimers were calculated by convolution of the voltammetric data and were similar to the theoretical charges for DAB-AM-n. For PAMAM, only the lowest generation exhibited reversible behavior, with higher generations having irreversible behavior. Using cyclic voltammetry, low micromolar concentrations of the dendrimers were detected. The results show that electrochemistry at the ITIES can be a useful method for characterization of ionizable dendrimers and that voltammetry can be a simple method for detection of low concentrations of these multicharged species.