# Surface-triggered cascade reactions between DNA linkers direct self-assembly of colloidal crystals of controllable thickness

## TL;DR

This paper introduces a surface-triggered DNA cascade reaction system that enables the controlled self-assembly of colloidal crystals with tunable thickness, combining experiments, simulations, and theory to elucidate the underlying thermodynamics.

## Contribution

It presents a novel mechanism where surfaces initiate DNA-mediated cascade reactions, allowing for the fabrication of finite, controllable-thickness colloidal structures.

## Key findings

- Surface interactions activate colloids for assembly.
- Thermodynamics of activation and binding are clarified.
- Finite aggregates with controllable layers can be formed.

## Abstract

Functionalizing colloids with reactive DNA linkers is a versatile way of programming self-assembly. DNA selectivity provides direct control over colloid-colloid interactions allowing the engineering of structures such as complex crystals or gels. However, self-assembly of localized and finite structures remains an open problem with many potential applications. In this work, we present a system in which functionalized surfaces initiate a cascade reaction between linkers leading to self-assembly of crystals with a controllable number of layers. Specifically, we consider colloidal particles functionalized by two families of complementary DNA linkers with mobile anchoring points, as found in experiments using emulsions or lipid bilayers. In bulk, intra-particle linkages formed by pairs of complementary linkers prevent the formation of inter-particle bridges and therefore colloid-colloid aggregation. However, colloids interact strongly with the surface given that the latter can destabilize intra-particle linkages. When in direct contact with the surface, colloids are activated, meaning that they feature more unpaired DNA linkers ready to react. Activated colloids can then capture and activate other colloids from the bulk through the formation of inter-particle linkages. Using simulations and theory, validated by existing experiments, we clarify the thermodynamics of the activation and binding process and explain how particle-particle interactions, within the adsorbed phase, weaken as a function of the distance from the surface. The latter observation underlies the possibility of self-assembling finite aggregates with controllable thickness and flat solid-gas interfaces. Our design suggests a new avenue to fabricate heterogeneous and finite structures.