Figure 1: Self-assembly pathway and experimental implementation of the two binary mixtures.

(a) From left to right, snapshots for an MD simulation of the two-step gelation process of an α–β mixture. α- and β-particles are coloured in red and green, respectively. Initially, colloidal interactions are repulsive and the system equilibrates into a uniform gas phase. The α–α attraction is switched on, and gelation occurs. Finally, the β–β attraction is activated and the β-phase aggregates in the confined environment imposed by the α-template-gel. (b) Experimental implementation of the α- and β-particles with DNACCs. α–α and β–β hybridization interactions are activated at temperatures T_α>T_β such that the two-step aggregation pathway can be induced upon quenching from T_in>T_α to T_α>T_mid>T_β and finally to T_fin<T_β. (c) From left to right, snapshots of an MD simulation of a core-shell gelation of a γ–δ mixture. γ-and δ-particles are coloured in red and blue, respectively. Initially, the γ–γ attraction is switched on, and forms a gel from the initially uniform gas phase. Upon activation of the γ–δ attraction, δ-particles coat the γ-gel as a single layer. δ–δ interactions are repulsive at every stage. (d) Experimental implementation of the γ–δ mixture with DNACCs. γ-colloids are functionalized with B and B′ sticky ends, giving rise to an intraspecies attraction for T<T_γ. δ-particles are coated only with B_S sticky ends, complementary to part of B′ (marked in red), such that a γ–δ attraction arises for T<T_δ<T_γ. The DNA constructs are grafted to the surface of the colloids via biotin–streptavidin bonds. To reduce the aggregation temperature of species α and γ, a fraction of the grafting sites is occupied by inert PEG polymers.