Engineering and Applications of DNA-Grafting Polymer Materials

Abstract

The emergence of hybrid materials combining biomacromolecules and organic polymers has received broad attention based on their potential applications in chemical, biological and materials sciences. Among different coupling strategies, the grafting of oligonucleotides to organic polymers as side chains by covalent bonds provides a novel platform whereby the properties of both oligonucleotides and polymer backbone are integrated, manipulated and optimized for various applications. In this review, we give the perspective on this specific type of DNA polymer hybrid materials , using selected examples with emphasis on bioanalysis, biomedicine and stimuli-responsive materials. It is expected the success of DNA-grafting polymers will not only impact the frabication of novel bimolecule incorporated materials, but also will influence how the properties of synthetic materials are tailored using different functional groups.

Figure 1

Synthesis of DNA-grafting polymers. A) Covalent modification of nucleic acids to polymers via coupling chemistry. B) Copolymerization of polymerizable group terminated nucleic acids with polymer monomers.

Figure 2

Examples of biosensors for DNA detection based on DNA-grafting polymers. A) Electrochemical detection of DNA employing a DNA–ferrocene–polymer hybrid (adapted from Ref. [24]. B) DNA detection using a light-emitting polymer immobilized on a chip surface (adapted from Ref. [48]).

Figure 3

A) Structure of DNA-poly(L-lysine) conjugate. (adapted from Ref. [53]) B) Temperature controlled binding of DNA-PNIPAM conjugate with target mRNA. (adapted from Ref. [55])

Figure 4

Aptamer-grafting acrylamide polymers for selective cytotoxicity. A) Scheme of polymeric aptamers. Selective cytotoxicity achieved with B) non-drug-resistant cancer cells and C) drug-resistant cells. (adapted from Ref. [26])

Figure 5

A) Target ssDNA induced swelling of semi-IPN DNA-grafting polymer hydrogel (adapted from Ref. [68]) B). Target ssDNA induced volume change of hairpin DNA (top) and DNA without secondary structure crosslinked polymer hydrogels. (adapted from Ref. [36])

Figure 6

A) Detection of adenosine using aptamer crosslinked hydrogels by sol-gel transition. (adapted from Ref. [73]) B) Signal amplified detection of targets based on colorimetric reaction catalyzed by enzymes released from target-responsive hydrogels (adapted from Ref. [77]). C) Detection of mersury ion using thymine-rich DNA-grafting polymer hydrogels. (adapted from Ref. [78])

Figure 7

Illustration of hydrogel swelling behaviors in response to complementary sequences monitored by the interferometric technique. (adapted from Ref. [82])

Figure 8

Colorimetric logic gates based on aptamer-crosslinked hydrogels: A) AND gate and B) OR gate using cocaine and ATP as stimuli. (adapted from Ref. [83])

Figure 9

Controlled release from DNA-crosslinked hydrogels. A) DNA induced release of QDs. (adapted from Ref. [89]) B) Light controlled release from photoresponsive DNA-crosslinked hydrogel. (adapted from Ref. [29] C) NIR light triggered thermal release from DNA nanogels coated on gold nanorods. (adapted from Ref. [37])

Figure 10

A) Light-controlled DNA hybridization. (B) Reversible volume transition of the DNA-crosslinked hydrogel regulated by UV and visible light. (adapted from Ref. [30])