Nanoscale patterning of polymers on DNA origami

Abstract

Structurally precise biohybrid nanomaterials were created by grafting various polymers to DNA with high conversions under ambient conditions. They are patterned onto DNA origami nanostructures to form customizable surface contours.

A Versatile and Efficient Method to Isolate DNA–Polymer Conjugates

“…DNA–polymer conjugates have seen a significant expansion in recent years due to the increasing accessibility of DNA, resulting in seminal developments ranging from gene therapy , to drug delivery − and biosensing. − Exploiting the fidelity of DNA technology, they can be used to construct sophisticated shapes and patterns that are only a few nanometers in size, leading to new possibilities for the design and construction of precision nanoscale devices. , Furthermore, functional polymer or polymer-coated DNA architectures lead to an enhanced cellular uptake, thereby increasing pharmaceutical applications, for instance as drug carriers. − Additionally, by varying the length and composition, they can provide diverse architectures including micelles, vesicles, and tubes . The individual control over the polymer and DNA length, composition, and chemical handles enables broad engineering of conjugate properties for targeted applications. , …”

“…To prepare DNA–polymer conjugates, the grafting-to method is commonly used, which involves using excess amounts of the less expensive polymer to achieve high conversion rates. ,− However, this often leads to the challenge of removing the unreacted polymer after the reaction. Because of the high amount of free polymer and the amphiphilic nature of the conjugates, spin filtration with molecular weight cutoffs often results in long purification times and major product loss .…”

“…To prepare DNA–polymer conjugates, the grafting-to method is commonly used, which involves using excess amounts of the less expensive polymer to achieve high conversion rates. ,− However, this often leads to the challenge of removing the unreacted polymer after the reaction. Because of the high amount of free polymer and the amphiphilic nature of the conjugates, spin filtration with molecular weight cutoffs often results in long purification times and major product loss . Other methods such as reversed-phase high performance liquid chromatography (HPLC) easily reach their capacity limits, requiring extensive optimization of the stationary and mobile phases according to different polymer scaffolds and molecular weights.…”

“…Subsequently, the polymer is covalently attached to a complementary functional group on the DNA block. In this case, the strategy was performed using NH 2 -functionalized oligonucleotide and NHS-activated polymers prepared by RAFT polymerization . The coupling was performed in a DMF/water (3:1) mixture using 50 equiv of the polymer, with DIPEA as an auxiliary base (Figure b).…”

“…7−9 Exploiting the fidelity of DNA technology, they can be used to construct sophisticated shapes and patterns that are only a few nanometers in size, leading to new possibilities for the design and construction of precision nanoscale devices. 10,11 Furthermore, functional polymer or polymer-coated DNA architectures lead to an enhanced cellular uptake, thereby increasing pharmaceutical applications, for instance as drug carriers. 12−14 Additionally, by varying the length and composition, they can provide diverse architectures including micelles, vesicles, and tubes.…”