This dissertation attempts to enhance understanding of charge transport dynamics in nanoscale systems that involve charged surfaces/interfaces. To do so, two platforms are studied which share foundational electrochemical concepts such as ion/electron transport, surface charge dependence as well as common voltammetric interrogation methods. The overall scheme of the dissertation is intended for the reader to gain familiarity with a theoretical and complex modeling platform and then be presented with an experimental application in which systemic complexity motivates the use of modeling to decouple contributing processes in multicomponent systems. The first system employs a numerical model of an interfacial membrane geometry to investigate the effect of space charge density and scan rate dependence. The second system attempts to characterize a complex sensing system by evaluating the isolated, component-level behavior of redox tags and reducing agents independently as well as when coupled and integrated into sensing platforms. This work is intended to be informational, not conclusive, or resolution-focused; rather, to improve upon current understanding of nanoscale platforms.