The presentation will briefly discuss our multidentate approach to create uniform metal nanoparticles by tailoring the core-ligand interactions. Exciting electrochemical and optical activities from sub-2-nm Au nanoparticles are reported. The talk will focus on novel mass transport behaviors through a single nanosized pipette or pore, analyzed by time and frequency domain electrochemical measurements and classic simulation. As the pore dimension miniaturizes and approaches that of a single bio-macromolecule, single molecule activities inside the mass transport limiting region perturb the ionic transport current thus be detected. Correlated with the well-known ion current rectification effect observed from various nanodevices, multitime-constant transport processes have been discovered. The knowledge allows us to differentiate the respective contribution to the current signal from substrate charges (coulomb interaction with fixed surface charges) and nanogeometry (volume effect). The transference number of cation and anion, and surface charge density of individual nanodevices, have been determined by combined experiments and simulation.