Using nickel to fold discrete synthetic macromolecules into single-chain nanoparticles

Macromolecules found in Nature display a precise control over the primary as well as higher ordered architectures. To mimic the folding found in Nature, we herein demonstrate the design and...

Reading mixtures of uniform sequence-defined macromolecules to increase data storage capacity

In recent years, the field of molecular data storage has emerged from a niche to a vibrant research topic. Herein, we describe a simultaneous and automated read-out of data stored in mixtures of sequence-defined oligomers. Therefore, twelve different sequence-defined tetramers and three hexamers with different mass markers and side chains are successfully synthesised via iterative Passerini three-component reactions and subsequent deprotection steps. By programming a straightforward python script for ESI-MS/MS analysis, it is possible to automatically sequence and thus read-out the information stored in these oligomers within one second. Most importantly, we demonstrate that the use of mass-markers as starting compounds eases MS/MS data interpretation and furthermore allows the unambiguous reading of sequences of mixtures of sequence-defined oligomers. Thus, high data storage capacity considering the field of synthetic macromolecules (up to 64.5 bit in our examples) can be obtained without the need of synthesizing long sequences, but by mixing and simultaneously analysing shorter sequence-defined oligomers.

Concurrent Control over Sequence and Dispersity in Multiblock Copolymers

<p>Controlling monomer sequence in synthetic macromolecules is a major challenge in polymer science and the order of building blocks has already been demonstrated to determine macromolecular folding, self-assembly and fundamental polymer properties. Dispersity is another key parameter in material design, with both low and high dispersity polymers displaying complementary properties and functions. However, synthetic approaches that can simultaneously control both sequence and dispersity remain experimentally unattainable. Here we report a simple, one pot, and rapid synthesis of sequence-controlled multiblocks with on demand control over dispersity while maintaining high livingness, excellent agreement between theoretical and experimental molecular weights and quantitative yields. Key to our approach is the regulation in chain transfer agent activity during controlled radical polymerization that enables the preparation of multiblocks with gradually ascending (<i>Ɖ</i>=1.16 →1.60), descending (<i>Ɖ</i>=1.66 →1.22), alternating low and high dispersity values (<i>Ɖ</i>=1.17 →1.61 →1.24 →1.70 →1.26) or any combination thereof. The enormous potential of our methodology was further demonstrated through the impressive synthesis of highly ordered pentablock, octablock and decablock copolymers yielding the first generation of multiblocks with concurrent control over both sequence and dispersity.</p>

Concurrent Control over Sequence and Dispersity in Multiblock Copolymers

<p>Controlling monomer sequence in synthetic macromolecules is a major challenge in polymer science and the order of building blocks has already been demonstrated to determine macromolecular folding, self-assembly and fundamental polymer properties. Dispersity is another key parameter in material design, with both low and high dispersity polymers displaying complementary properties and functions. However, synthetic approaches that can simultaneously control both sequence and dispersity remain experimentally unattainable. Here we report a simple, one pot, and rapid synthesis of sequence-controlled multiblocks with on demand control over dispersity while maintaining high livingness, excellent agreement between theoretical and experimental molecular weights and quantitative yields. Key to our approach is the regulation in chain transfer agent activity during controlled radical polymerization that enables the preparation of multiblocks with gradually ascending (<i>Ɖ</i>=1.16 →1.60), descending (<i>Ɖ</i>=1.66 →1.22), alternating low and high dispersity values (<i>Ɖ</i>=1.17 →1.61 →1.24 →1.70 →1.26) or any combination thereof. The enormous potential of our methodology was further demonstrated through the impressive synthesis of highly ordered pentablock, octablock and decablock copolymers yielding the first generation of multiblocks with concurrent control over both sequence and dispersity.</p>