To study slow mass transport in confined environments, we developed a three-dimensional (3D) single-particle localization technique to track their microscopic movements in cylindrical nanopores. Under two model conditions, particles are retained much longer inside the pores: (1) increased solvent viscosity, which slows down the particle throughout the whole pore, and (2) increased pore wall affinity, which slows down the particle only at the wall. In viscous solvents, the particle steps decrease proportionally to the increment of the viscosity, leading to macroscopically slow diffusion. As a contrast, the particles in sticky pores are microscopically active by showing limited reduction of step sizes. A restricted diffusion mode, possibly caused by the heterogeneous environment in sticky pores, is the main reason for macroscopically slow diffusion. This study shows that it is possible to differentiate slow diffusion in confined environments caused by different mechanisms.
Early studies showed that the adsorption of nanorods may start from a special "anchored" state, in which the nanorods lose translational motion but retain rotational freedom. Insight into how the anchored nanorods rotate should provide additional dimensions for understanding particle-surface interactions. Based on conventional time-resolution studies, gold nanorods are thought to continuously rotate following initial interactions with negatively charged glass surfaces. However, this nanosecond time-resolution study reveals that the apparent continuous rotation actually consists of numerous fast, intermittent rotations or transitions between a small number of weakly immobilized states, with the particle resting in the immobilized states most of the time. The actual rotation from one immobilized state to the other happens on a 1 ms timescale, that is, approximately 50 times slower than in the bulk solution.
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