Abstract

DNA is the key biomolecule central to almost all processes in living organisms. The eccentric idea of utilizing DNA as a material building block in molecular and structural engineering led to the creation of numerous molecular-assembly systems and materials at the nanoscale. The molecular structure of DNA is believed to have evolved over billions of years, with structure and stability optimizations that allow life forms to sustain through the storage and transmission of genetic information with fidelity. The nanoscale structural characteristics of DNA (2 nm thickness and ca. 40–50 nm persistence length) have inspired the creation of numerous functional patterns and architectures through noncovalent conventional and unconventional base pairings as well as through mutual templating-interactions with small organic molecules and metal ions. The recent advancements in structural DNA nanotechnology allowed researchers to design new DNA-based functional materials with chemical and biological properties distinct from their parent components. The modulation of structural and functional properties of hybrid DNA ensembles of small functional molecules (SFMs) and short oligonucleotides by adapting the principles of molecular architectonics enabled the creation of novel DNA nanoarchitectures with potential applications, which has been termed as templated DNA nanotechnology or functional DNA nanoarchitectonics. This review highlights the molecular architectonics-guided design principles and applications of the derived DNA nanoarchitectures. The advantages and ability of functional DNA nanoarchitectonics to overcome the trivial drawbacks of classical DNA nanotechnology to fulfill realistic and practical applications are highlighted, and an outlook on future developments is presented.

Highlights

  • The development of functional molecular systems and materials on a nanoscale through custom design and engineering of molecular organization is a highly attractive concept in materials science [1,2]

  • While DNA nanotechnology is extremely creative in its original form and produced complex nanoarchitectures of virtually any shape and size through standard and robust DNA self-assembly, potential applications of these materials are yet be realized. In this context, templated DNA nanotechnology or functional DNA nanoarchitectonics have been conceived to overcome the limitations of classical DNA nanotechnology

  • Templated coassemblies of small functional molecules (SFMs) and ssDNA were orchestrated through conventional (WC) and unconventional hydrogen bonding, aromatic π–π stacking, electrostatic, and metal coordination-based interactions

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Summary

Introduction

The development of functional molecular systems and materials on a nanoscale through custom design and engineering of molecular organization is a highly attractive concept in materials science [1,2]. The molecular stability, predictable sequence specificity, molecular recognition properties, and the formation of regular and defined structures of DNA made it possible to custom the design and to engineer a range of molecular architectures [5,6,7,8,9]. The nanoscale structural features of DNA have inspired the design of diverse functional architectures utilizing both conventional and unconventional base pairing along with the mutually templating interactions of SFMs and metal ions [12]. The field of DNA nanotechnology has evolved over the years from using DNA tiles and blocks to employing SFMs and their assemblies as templates to control the molecular organization on the nanoscale to generate complex DNA architectures or origami and hybrid ensembles, respectively, through the judicious exploitation of conventional and nonconventional base pairing interactions [12,13]

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