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.

A DNA synthesizer was successfully employed for preparation of well-defined polymers by atomtransfer 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. BothCorrespondence to: Subha R. Das; Krzysztof Matyjaszewski. + These authors contributed equally to this work. Conflict of interestThe authors declare no conflict of interest.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under http://dx.doi.org/ 10.1002/anie.201611567. HHS Public Access Author ManuscriptAuthor Manuscript Author ManuscriptAuthor Manuscript 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. AutoradPhotoinduced atom-transfer radical polymerization is conducted in an automated DNA synthesizer to prepare well-defined homopolymers, diblock copolymers, and biohybrids. This technique provides a clean polymerization system under ambient temperature with oxygen tolerance. KeywordsDNA; photochemistry; polymerization; structure determination; synthetic methods Atom-transfer radical polymerization (ATRP) has transformed polymer synthesis by providing a robust route for the preparation of well-defined polymers with precisely controlled molecular weight (MW), narrow molecular weight distribution (M w /M n ), and designed architectures. [1] ATRP has also been successfully applied to the preparation of a diverse range of biological conjugates, including DNA-polymer hybrids, [2] protein-polymer hybrids, [3] and polysaccharide polymer conjugates. [4] These bioconjugates show properties which could potentially be used as biological sensors or drug delivery agents. [5] However, discovery, utilization, and tuning the functionality of these materials to prepare a broad spectrum of biohybrids for evaluation in a specific application has been limited by tedious synthetic efforts and tremendous labor cost. Automated synthesizers overcame this obstacle in the synthesis of peptides, [6] oligonucleotides, [7] and oligosaccharides. [8] A synthetic strategy based on general building blocks and protection/deprotection/coupling cycles using an automated synthesis platform was also expanded to the synthesis of small organic molecules [9] and sequence-coded polymers. [10] Given the widespread success of these approaches to automa...

Highlights d Simulations and experiments provide insight into how LARP1 binds TOP mRNA d Key residues contribute to cap recognition dynamics and mRNA specificity d Druggable LARP1 pockets suggest avenues for anti-cancer drug discovery

Particularly for its use in bioconjugations, the copper-catalyzed (or promoted) azide-alkyne cycloaddition (CuAAC) reaction or ‘click chemistry’, has become an essential component of the modern chemical biologist’s toolbox. Click chemistry has been applied to DNA, and more recently, RNA conjugations, and the protocol presented here can be used for either. The reaction can be carried out in aqueous buffer and uses acetonitrile as a minor co-solvent that serves as a ligand to stabilize the copper. The method also includes details on the analysis of the reaction product.

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