Localized Template‐Driven Functionalization of Nanoparticles by Dynamic Combinatorial Chemistry

Abstract

We have developed a method for the localized functionalization of gold nanoparticles using imine-based dynamic combinatorial chemistry. By using DNA templates, amines were grafted on the aldehyde-functionalized nanoparticles only if and where the nanoparticles interacted with the template molecules. Functionalization of the nanoparticles was controlled solely by the DNA template; only amines capable of interacting with DNA were bound to the surface. Interestingly, even though our libraries contained only a handful of simple amines, the DNA sequence influenced their attachment to the surface. Our method opens up new opportunities for the synthesis of multivalent, nanoparticle-based receptors for biomacromolecules.

Dynamic Expression of DNA Complexation with Self‐assembled Biomolecular Clusters

“…However,f ew examples exploit as elf-assembly approach based on DCC. [21] We report herein the implementation of as elf-assembly approach using DCC for the in situ generation of biomolecular clusters that effectively complex dsDNAt hrough multivalent interactions.S uch ad ynamic self-assembly approach, using ar eversible reaction compatible with the presence of the DNAtarget, should enable realtime monitoring of DNAc omplexation as the self-assembly proceeds and leads to an increase of valency. [19] More recently,i mines were used for DNAr ecognition by dynamic constitutional frameworks [20] and functionalized nanoparticles.…”

Dynamic Covalent Nanoparticle Building Blocks

“…Independently, Otto and co‐workers have exploited kinetically facile imine exchange to achieve template‐driven dynamic covalent NP functionalisation (Figure ) . On treating AuNP‐ 12 / 13 ( d ≈11.7 nm), which is stabilised by a mixed monolayer incorporating approximately 10 mol % aldehyde ligand 12 , with mixtures of simple primary amines, negligible NP‐bound imine formation was observed.…”

“…This could be explained by thermodynamic stabilisation of NP‐bound imines as a result of multivalent interactions between the imine‐functionalised NP surface and the oligonucleotide template. Significantly, the degree of functionalisation, and the composition of NP‐bound imine libraries, depended on the oligonucleotide sequence employed (Figure b): the dynamic covalent ligand shell can adapt to optimise binding to each specific DNA template . Very recently, the same approach was extended to the formation of NP‐bound hydrazones, whereby mixtures of two different NP‐bound hydrazones were obtained depending on the DNA template sequence .…”

“… a) DNA‐templated dynamic covalent AuNP‐bound imine monolayers; negligible imine formation occurs in the absence of DNA; b) monolayer composition depends on the specific base pair sequence of the double‐stranded DNA template . Panel (b) adapted with permission from ref.…”

Dynamic combinatorial chemistry on a monolayer protected gold nanoparticle

“…15, 16 Here, we apply DCC on a monolayer protected gold nanoparticle (Au NP) and show that the surface composition spontaneously adapts to the added target (Hg 2+ or 35 Ag + ). 17 In the past years we have exploited the interaction between Au NP 1 and oligoanions for the development of sensing and catalytic systems. 18,19 Au NP 1 are gold nanoparticles (d = 1.8 ± 0.4 nm) covered with hydrophobic C9-thiols terminating 40 with a 1,4,7-triazacyclononane (TACN)•Zn 2+ head group (Fig.…”