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. 2017 Mar 1;56(10):2740-2743.
doi: 10.1002/anie.201611567. Epub 2017 Feb 6.

Automated Synthesis of Well-Defined Polymers and Biohybrids by Atom Transfer Radical Polymerization Using a DNA Synthesizer

Xiangcheng Pan  1 , Sushil Lathwal  2 , Stephanie Mack  2 , Jiajun Yan  1 , Subha R Das  2 , Krzysztof Matyjaszewski  1
Affiliations

Automated Synthesis of Well-Defined Polymers and Biohybrids by Atom Transfer Radical Polymerization Using a DNA Synthesizer

Xiangcheng Pan et al. Angew Chem Int Ed Engl. .

Abstract

A DNA synthesizer was successfully employed for preparation of well-defined polymers by atom transfer radical polymerization (ATRP), in a technique termed AutoATRP. This method provides well-defined homopolymers, diblock copolymers, and biohybrids under automated photomediated ATRP conditions. PhotoATRP was selected over other ATRP methods because of mild reaction conditions, ambient temperature, tolerance to oxygen, and no need to introduce reducing agents or radical initiators. Both acrylate and methacrylate monomers were successfully polymerized with excellent control in the DNA synthesizer. Diblock copolymers were synthesized with different targeted degrees of polymerization and with high retention of chain-end functionality. Both hydrophobic and hydrophilic monomers were grafted from DNA. The DNA-polymer hybrids were characterized by SEC and DLS. The AutoATRP method provides an efficient route to prepare a range of different polymeric materials, especially polymer-biohybrids.

Keywords: DNA; photochemistry; polymerization; structure determination; synthetic methods.

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Conflict of interest statement

Conflict of interest

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Results for polymerization of BA by AutoATRP in the synthesizer (entry 1, Table 1) under the following reaction conditions: [BA]0/[EBiB]0/[CuBr2]0/[Me6TREN]0 = 100:1:0.03:0.18, 50% MeCN (v%), irradiation by three optical fibers (3 × 50 mWcm−2, 365 nm) at ambient temperature. a) Semilogarithmic kinetic plot. b) Evolution of molecular weight and molecular weight distribution. c) SEC traces evolution.
Figure 2
Figure 2
SEC traces of block copolymers of MA-b-EA at different targeted degrees of polymerization in DMSO with UV irradiation. Gray line: SEC trace of PMA, black line: SEC trace of PMA-b-EA.
Figure 3
Figure 3
a) Synthetic scheme for of DNA-polymer hybrids in the automated synthesizer under photoATRP conditions: [Monomer]0/[iBBr-SeqAA]0/[CuBr2]0/[Me6TREN]0 = 1000:1:0.5:3, in DMSO with UV irradiation. b) GPC traces for SeqAA-b-POEOA from iBBr-SeqAA. c) DLS data of SeqAA-b-PMA.
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