The electrochemical ion-transfer reactivity of porphyrinato metal complexes in 4-(3-phenylpropyl)pyridine | water systems

Spectroelectrochemical Investigation of TPPMn(III/II)‐Driven Liquid | Liquid | Electrode Triple Phase Boundary Anion Transfer into 4‐(3‐Phenylpropyl)‐Pyridine: ClO4−, CO3H−, Cl−, and F−

“…For the case of ClO 4 À transfer simple Nernstian conditions prevail. A midpoint potential of E mid = 1/2 (E p ox + E p red ) = À0.3 V vs. SCE is observed consistent with previous reports [20]. At lower scan rates (see Figure 2 B) the voltammetric response can be seen to become increasingly symmetric consistent with thin layer electrolysis and conversion of material throughout the deposit.…”

“…interacting redox systems, in particular with ferrocene derivatives [18] and with TPP-lutetium complexes [19]. For the TPPMn(III/II) redox system in 4-(3-phenylpropyl)-pyridine (PPP) the likelihood of axial coordination of an anion (replacing an axial pyridine) is considerable for the more nucleophilic anions such as fluoride or cyanide and evidence for some weak coordination has been reported for examples based on voltammetry evidence [20]. However, in order to further explore mechanistic details such as ligand exchange and coordination to the metal centre, additional experimental probes such as spectroelectrochemistry are desirable.…”

“…The new process at more negative potentials is present in particular in the "preoxidised state" of the electrode with TPPMn(III) + as the soluble redox species in the presence of fluoride. The new more negative redox process can be identified as a cation (here sodium) transfer (Equation 7) [20].…”

Voltammetric Insights in the Transfer of Ionizable Drugs Across Biomimetic Membranes - Recent Achievements

“…Inverse experiments for the evaluation of lipophilic parameters in water droplets immobilized on organic electrodes subsequently submersed into organic electrolyte solutions have also been used [43]. Other recent and important contributions in the field of ionic drug transfer studies, obtained by using the three-phase electrode, were reported by Opalo and Marken et al [44][45][46][47][48], Karyakin et al [49][50][51], Pereira et al [52], and Mirceski et al [53,54]. Detailed information on the application and fundaments of the threephase electrode process can be find in reviews by Scholz et al [7,8] and Marken [6] reviews.…”

“…Shao and Pereira et al [78] reported, for first time, the polarization of a nano-interface between water and n-octanol by using a modified version of the classical four electrode voltammetry at ITIES. Additionaly, nitrophenyloctyl ether (NPOE) emerged as a viable non-toxic organic solvent in experiments at the polarized liquid-liquid interface [5,9,37,44,46,[79][80][81][82]. NPOE has a moderate dielectric constant and a high viscosity that makes it a good ionic solvent suitable for kinetic studies.…”