Colloidal crystal engineering with metal\u2013organic framework nanoparticles and DNA

Shunzhi Wang,Sarah S Park,Cassandra T Buru,Eric W Roth,Chad A Mirkin,Haixin Lin,Omar K Farha,Peng-Cheng Chen

doi:10.1038/s41467-020-16339-w

Shunzhi Wang, Sarah S Park + Show 6 more

Open Access

https://doi.org/10.1038/s41467-020-16339-w

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Journal: Nature Communications	Publication Date: May 19, 2020
Citations: 116	License type: open-access

Affiliation: Northwestern University

Abstract

Colloidal crystal engineering with nucleic acid-modified nanoparticles is a powerful way for preparing 3D superlattices, which may be useful in many areas, including catalysis, sensing, and photonics. To date, the building blocks studied have been primarily based upon metals, metal oxides, chalcogenide semiconductors, and proteins. Here, we show that metal–organic framework nanoparticles (MOF NPs) densely functionalized with oligonucleotides can be programmed to crystallize into a diverse set of superlattices with well-defined crystal symmetries and compositions. Electron microscopy and small-angle X-ray scattering characterization confirm the formation of single-component MOF superlattices, binary MOF–Au single crystals, and two-dimensional MOF nanorod assemblies. Importantly, DNA-modified porphyrinic MOF nanorods (PCN-222) were assembled into 2D superlattices and found to be catalytically active for the photooxidation of 2-chloroethyl ethyl sulfide (CEES, a chemical warfare simulant of mustard gas). Taken together, these new materials and methods provide access to colloidal crystals that incorporate particles with the well-established designer properties of MOFs and, therefore, increase the scope of possibilities for colloidal crystal engineering with DNA.

Highlights

Colloidal crystal engineering with nucleic acid-modified nanoparticles is a powerful way for preparing 3D superlattices, which may be useful in many areas, including catalysis, sensing, and photonics
Unlike the surfaces of conventional inorganic NPs, which are typically capped with organic ligands, a mixture of positively charged metals and negatively charged ligands are exposed at the surfaces of as-synthesized Metal–organic frameworks (MOFs) NPs34
Having shown that DNA and the design rules afforded by the complementary contact model can be used to engineer MOF programmable atom equivalents (PAEs) colloidal crystals, we explored whether metal–organic framework nanoparticles (MOF NPs) shape can be used to access more exotic crystalline states

Summary

Introduction

Colloidal crystal engineering with nucleic acid-modified nanoparticles is a powerful way for preparing 3D superlattices, which may be useful in many areas, including catalysis, sensing, and photonics. We describe a density gradient centrifugation-based method for obtaining monodisperse samples of MOF NPs, employ a straightforward coordinative strategy for chemically modifying them with DNA at a density sufficient to support their programmed crystallization, and explore how they can be assembled deliberately into superlattices based upon insight from the complementary contact model (Fig. 1)[8].

Results

Conclusion