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In this article, we study the size-dependent interactions of quasi-spherical nanocrystals with voids of concave nanoparticles of complementary sizes and shapes. Experimental insights into a system with key and lock particles with smaller dimensions than 15 nm are presented, which provide evidence for key-lock specific interaction on this length scale. Using depletion attraction as a driving force, the key-lock interaction is shown to be reversible and independent of the material composition of the key particles. Poly(ethylene glycol) methacrylate was utilized as a depletion agent in toluene, the solvent of the studied key-lock system. For this work, a model system of specifically developed concave manganese oxide nanocrystals, synthesized via a cast-mold approach, in combination with highly monodisperse quasi-spherical gold nanocrystals, was investigated with transmission electron microscopy, optical UV/vis/NIR spectroscopy and powder X-ray diffraction. Size-dependent key-lock interactions are clearly identified to occur. For geometrical reasons, only key particles with smaller particle diameters than the voids of the complementary lock particles are able to enter the void. So the void diameter of the lock particles sets a diameter threshold for the key-lock interaction. Additionally, other key particles like silver, iron oxide and even core-shell structured gold-nickel sulfide nanocrystals show key-in-lock assemblies with concave manganese oxide nanocrystals. This behaviour might open up new routes for size-selective particle sensing.

The size-selective interaction of key and lock nanocrystals driven by depletion attraction at the nanoscale