Non‐Biochemical Gradient Sequence‐Controlled Polymers with Tuned Kinetics and Self‐Assembled Morphologies

Two key challenges in the multidisciplinary field of sequence-controlled polymers are their efficient synthesis and the establishment of correlation with polymer properties. In this context, in this paper, gradient architecture in the hydrophobic tail of an amphiphile is implemented and synthesized for a fixed hydrophilic unit (polyethylene glycol, PEG), by means of two monomers (2-hydroxypropyl methacrylate, HPMA, and diacetone acrylamide, DAAM) of contrasting reactivities. The resulting non-biochemical gradient sequence-controlled polymers are generated from a one-pot, homogeneous mixture through a PET-RAFT-PISA (photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer-polymerization-induced self-assembly) method. In addition, the initial concentration ratio of the monomers in the gradient is varied as an input for a set of fixed experimental parameters and conditions, and its correlation with kinetics, gradient and self-assembled morphologies is established, as the output of the process. These results are extensively corroborated via nuclear magnetic resonance (NMR) spectroscopy analysis, together with transmission electron microscopy (TEM) images, dynamic light scattering (DLS), and gel permeation chromatography (GPC) experiments. These results have implications for chemical computation carried out by PISA, programmable self-assembly, information storage, biomimetics, origins of life and synthetic protocell studies.