Electrostatically Directed Long‐Range Self‐Assembly of Nucleotides with Cationic Nanoparticles To Form Multifunctional Bioplasmonic Networks

Abstract

Precise control over interparticle interactions is essential to retain the functions of individual components in a self-assembled superstructure. Here, we report the design of a multifunctional bioplasmonic network via an electrostatically directed self-assembly process involving adenosine 5'-triphosphate (ATP). The present study unveils the ability of ATP to undergo a long-range self-assembly in the presence of cations and gold nanoparticles (AuNP). Modelling and NMR studies gave a qualitative insight into the major interactions driving the bioplasmonic network formation. ATP-Ca 2 + coordination helps in regulating the electrostatic interaction, which is crucial in transforming an uncontrolled precipitation into a kinetically controlled aggregation process. Remarkably, ATP and AuNP retained their inherent properties in the multifunctional bioplasmonic network. The generality of electrostatically directed selfassembly process was extended to different nucleotidenanoparticle systems.

When Design Meets Function: The Prodigious Role of Surface Ligands in Regulating Nanoparticle Chemistry

“…41,68 As expected, the strong electrostatic attraction between [+] AuNP and [−] ATP resulted in an uncontrolled aggregation and precipitation process (marked as "State 8" in Figure 1). 41,69 During this process, the plasmonic property of AuNP was completely lost�a typical example of the loss of inherent property. This uncontrolled precipitation process (static self-assembly) was transformed into a controlled self-assembly process by regulating the way the two components interact with each other.…”

“…This is because of the sensitive nature of NPs and biomolecules and the lack of control over the interparticle interactions during the aggregation process. However, a recent set of studies have proved that a fine-tuning of interparticle interactions can not only retain but also result in a synergy between the inherent properties of the AuNP and biomolecule. , As expected, the strong electrostatic attraction between [+] AuNP and [−] ATP resulted in an uncontrolled aggregation and precipitation process (marked as “State 8” in Figure ). , During this process, the plasmonic property of AuNP was completely losta typical example of the loss of inherent property.…”

“…In a separate study by our group, divalent cations were used as the salt to screen the charges and regulate the electrostatic interaction between the AuNP and ATP. 41 The kinetics of the aggregation process was slow enough (∼15 days) to form a long-range self-assembled structure between the AuNP and ATP. The highlight of our approach was the retention of the inherent properties of the individual components, along with a synergy between the AuNP and ATP in catalyzing an oxidation reaction.…”

“…Depending on the pathway adopted, the self-assembly process can lead to the formation of NP precipitate (marked as “State 8”), well-ordered 3D microcrystals (marked as “State 9”), and a bioplasmonic network (marked as “State 10”). Parts adapted with permission from ref and ref . Copyright 2022 John Wiley and Sons and Copyright 2006 American Association for the Advancement of Science.…”

“…There are a few robust protocols available for the functionalization of the “ligand of choice” on the surface of a small set of nanomaterials, without losing the inherent core properties. − As a result, the majority of “ligand-directed studies” are limited to this small set of nanomaterials, including plasmonic (Au and Ag), semiconductor (metal oxides, carbon dots, and quantum dots), and magnetic (Fe 3 O 4 ) nanoparticles. − With this limited set of NPs, our group and others have shown that the concept of a ligand-directed interplay of forces and interactions not only can improve the existing NP functions but can impart newer properties as well. − ,− This perspective summarizes the impact of such fine-tuned interparticle interactions, emanating from the surface ligands, in three important areas of nanoscience: self-assembly, (photo)­catalysis, and photophysics (Scheme ). The diversity in the properties benefited itself proves the breadth and depth of the impact that “ligand of choice” and interparticle interactions can have in material science.…”