RESUMEN
An ongoing challenge in polymer chemistry is accessing diverse block copolymers from multiple polymerization mechanisms and monomer classes. One strategy to accomplish this goal without intermediate compatibilization steps is the use of universal mediators. Thiocarbonyl thio (TCT) functional groups are well-known mediators to combine radical with either cationic or anionic polymerization, but a sequential cationic-anionic universal mediator system has never been reported. Herein, we report a TCT universal mediator that can sequentially perform photocontrolled cationic polymerization and thioacyl anionic group transfer polymerization to access poly(ethyl vinyl ether)-block-poly(thiirane) polymers for the first time. Thermal analyses of these block copolymers provide evidence of microphase separation. The success of this system, along with the established compatibility of radical polymerization, enabled us to further chain extend the cationic-anionic diblock using radical polymerization of N-isopropylacrylamide. The resulting terpolymer represents the first example of a triblock made from three different monomer classes incorporated via three different mechanisms without any end-group modification steps. The development of this simple, sequential synthesis using a universal mediator approach opens up new possibilities by providing facile access to diverse block copolymers of vinyl ethers, thiiranes, and acrylamides.
RESUMEN
The ribosome is a macromolecular machine that catalyzes the sequence-defined polymerization of L-α-amino acids into polypeptides. The catalysis of peptide bond formation between amino acid substrates is based on entropy trapping, wherein the adjacency of transfer RNA (tRNA)-coupled acyl bonds in the P-site and the α-amino groups in the A-site aligns the substrates for coupling. The plasticity of this catalytic mechanism has been observed in both remnants of the evolution of the genetic code and modern efforts to reprogram the genetic code (e.g., ribosomal incorporation of non-canonical amino acids, ribosomal ester formation). However, the limits of ribosome-mediated polymerization are underexplored. Here, rather than peptide bonds, we demonstrate ribosome-mediated polymerization of pyridazinone bonds via a cyclocondensation reaction between activated γ-keto and α-hydrazino ester monomers. In addition, we demonstrate the ribosome-catalyzed synthesis of peptide-hybrid oligomers composed of multiple sequence-defined alternating pyridazinone linkages. Our results highlight the plasticity of the ribosome's ancient bond-formation mechanism, expand the range of non-canonical polymeric backbones that can be synthesized by the ribosome, and open the door to new applications in synthetic biology.