Synthetic chemists have devoted tremendous effort towards the production of precision synthetic polymers with defined sequences and specific functions. However, the creation of a general technology that enables precise control over monomer sequence, with efficient isolation of the target polymers, is highly challenging. Here, we report a robust strategy for the production of sequence-defined synthetic polymers through a combination of liquid-phase synthesis and selective molecular sieving. The polymer is assembled in solution with real-time monitoring to ensure couplings proceed to completion, on a three-armed star-shaped macromolecule to maximize efficiency during the molecular sieving process. This approach is applied to the construction of sequence-defined polyethers, with side-arms at precisely defined locations that can undergo site-selective modification after polymerization. Using this versatile strategy, we have introduced structural and functional diversity into sequence-defined polyethers, unlocking their potential for real-life applications in nanotechnology, healthcare and information storage.
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All data that support the findings of this study are included within the Article and its Supplementary Information, and are also available from the authors upon request.
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This work was supported financially by the Engineering and Physical Sciences Research Council (EPSRC, EP/M003949/1) and GlaxoSmithKline. The authors acknowledge the EPSRC UK National Mass Spectrometry Facility at Swansea University for MALDI–TOF–MS measurements. The authors thank R. T. Woodward for GPC analysis and C. Yu for molecular modelling. The authors thank Huntsman for provision of Jeffamines.
Imperial Innovations has filed a UK patent application (no. 1516067.4) related to defined monomer sequence polymers (leading to PCT/GB2016/052801). A.G.L., P.R.J.G., R.D., R.C., P.M. and R.L. are listed as inventors. All other authors declare no competing interests.
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Dong, R., Liu, R., Gaffney, P.R.J. et al. Sequence-defined multifunctional polyethers via liquid-phase synthesis with molecular sieving. Nature Chem 11, 136–145 (2019) doi:10.1038/s41557-018-0169-6
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