Theoretical and Computational Chemistry

Structure and Dynamics of Adsorbed Dopamine on Solvated Carbon Nanotubes and in a CNT Groove



Advanced carbon microelectrodes are being developed for the in vivo detection of neurotransmitters, such as dopamine (DA), including many carbon nanotube (CNT) based electrodes. Our prior simulations of DA and dopamine-o-quinone (DOQ) on pristine, flat graphene showed rapid surface diffusion for all adsorbed species, but it is not known how CNT surfaces affect dopamine adsorption and surface diffusivity. In this work, we use molecular dynamics simulations to investigate the adsorbed structures and surface diffusion dynamics of DA and DOQ on CNTs of varying curvature and helicity. In addition, we study DA dynamics in a groove between two aligned CNTs to model the spatial constraints at the junctions within CNT assemblies. We find that the adsorbate diffusion on a solvated CNT surface depends upon curvature. However, this effect cannot be attributed to changes in the surface energy roughness because the lateral distributions of the molecular adsorbates are similar across curvatures, diffusivities on zigzag and armchair CNTs are indistinguishable, and the curvature dependence disappears in the absence of solvent. Instead, adsorbate diffusivities correlate with the vertical placement of the adsorbate's moieties, its tilt angle, its orientation along the CNT axis, and the number of waters in its first hydration shell -- all of which will influence its effective hydrodynamic radius. Finally, DA diffuses into and remains in the groove between a pair of aligned and solvated CNTs, enhancing diffusivity along the CNT axis. These first studies of surface diffusion on a CNT electrode surface are important for understanding the changes in diffusion dynamics of dopamine on nanostructured carbon electrode surfaces.


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Supplementary material

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Supplemental Information
Supplemental Information for ``Structure and Dynamics of Adsorbed Dopamine on Solvated Carbon Nanotubes and in a CNT Groove"