Colloidal Crystals Engineered with DNA from Supramolecular Programmable Atom Equivalents with Stimuli-Responsive...

Area of Science:

• Materials Science
• Nanotechnology
• Supramolecular Chemistry

Background:

• Colloidal crystal engineering relies on DNA-functionalized nanoparticles (programmable atom equivalents or PAEs).
• Traditional methods use DNA-DNA interactions to direct colloidal crystallization.
• A need exists for alternative strategies to control these self-assembling systems.

Purpose of the Study:

• To synthesize and characterize novel micellar PAEs based on DNA-modified perylene diimides.
• To investigate the assembly of these micellar PAEs with gold nanoparticle PAEs into colloidal crystals.
• To explore chemical stimuli for modulating colloidal crystal structures.

Main Methods:

• Synthesis and characterization of DNA-modified perylene diimide micellar PAEs.
• Assembly with gold nanoparticle PAEs to form colloidal crystals.
• Structural analysis using electron microscopy, UV-vis spectroscopy, and synchrotron small-angle X-ray scattering.
• Investigation of disassembly using anionic aromatic molecules.
• Computational modeling including molecular dynamics and first-principles calculations.

Main Results:

• Spherical micellar PAEs were successfully synthesized and characterized.
• These micellar PAEs assembled with gold nanoparticle PAEs into Body-Centered Cubic (BCC) colloidal crystal lattices.
• Anionic aromatic molecules were shown to disrupt micellar PAEs, leading to colloidal crystal disassembly.
• Computational studies indicated that PAE core assembly is independent of DNA valency and sequence.

Conclusions:

• Introduced a new class of micellar PAEs for colloidal crystal engineering.
• Demonstrated a novel strategy for controlling colloidal crystal structures via external chemical stimuli.
• Highlighted the potential for precise modulation of self-assembled nanomaterials.