The ability to functionalize nanoparticles with dense layers of highly oriented oligonucleotides has led to their use in programmable materials assembly, biomedicine, especially biodetection, gene regulation, and immune modulation, and beyond. To date, symmetrically functionalized nanostructures have primarily been synthesized and investigated, but the ability to prepare nanoparticles asymmetrically functionalized with multiple chemical functionalities at particular areas of their surfaces would represent a significant advance. Herein, we report a template-based approach for the face-selective chemical modification of nanorod surfaces with oligonucleotides. Nanorods of different compositions (e.g., Au, Ni) and tailorable dimensions were electrochemically synthesized within a porous anodic aluminum oxide template. The surfaces of the core segments of these stripped nanorods were isolated from each other by the template pore walls (sides) and the other metal components (ends). Then, either the template or the sacrificial segments were chemically removed to expose the rod surfaces individually (ends versus sides) by taking advantage of the varying chemistries of the components. Onto the selectively exposed surfaces, oligonucleotides were immobilized and utilized for the preparation of asymmetric assemblies and in therapeutic applications, where single nanostructures were employed to carry different molecular cargos on different surfaces.

Orthogonal chemical modification of template-synthesized nanostructures with oligonucleotides

255th National Meeting (2018)

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