Cyclopropenimine-Mediated CO2 Activation for the Synthesis of Polyurethanes and Small-Molecule Carbonates and Carbamates.

Carbon dioxide (CO2) is an abundant C1 feedstock with tremendous potential to produce versatile building blocks in synthetic applications. Given the adverse impact of CO2 on the atmosphere, it is of paramount importance to devise strategies for upcycling it into useful materials, such as polymers and fine chemicals. To activate such stable molecule, superbases offer viable modes of binding to CO2. In this study, a superbase cyclopropenimine derivative was found to exhibit exceptional proficiency in activating CO2 and mediating its polymerization at ambient temperature and pressure for the synthesis of polyurethanes. The versatility of this reaction can be extended to monofunctional amines and alcohols, yielding a variety of functional carbonates and carbamates.

Semiautomated synthesis of sequence-defined polymers for information storage.

Accelerated and parallel synthesis of sequence-defined polymers is an utmost challenge for realizing ultrahigh-density storage of digital information in molecular media. Here, we report step-economical synthesis of sequence-defined poly(l-lactic-co-glycolic acid)s (PLGAs) using continuous flow chemistry. A reactor performed the programmed coupling of the 2-bit storing building blocks to generate a library of their permutations in a single continuous flow, followed by their sequential convergences to a sequence-defined PLGA storing 64 bits in four successive flows. We demonstrate that a bitmap image (896 bits) can be encoded and decoded in 14 PLGAs using only a fraction of the time required for an equivalent synthesis by conventional batch processes. Accelerated synthesis of sequence-defined polymers could also contribute to macromolecular engineering with precision comparable to natural precedents.

Silicon incorporation in polymethine dyes.

Methods to red-shift fluorophores have garnered considerable interest due to the broad utility of low energy light. The incorporation of silicon into xanthene and coumarin scaffolds has resulted in an array of visible and near-infrared fluorophores. Here, we extend this approach to polymethine dyes, another popular fluorophore class, performing experimental and computational analyses. We found that when oxygen was replaced with SiMe2, bathochromic shifts of up to 121 nm and fluorophores with emission above 900 nm were achieved.

High-density information storage in an absolutely defined aperiodic sequence of monodisperse copolyester.

Synthesis of a polymer composed of a large discrete number of chemically distinct monomers in an absolutely defined aperiodic sequence remains a challenge in polymer chemistry. The synthesis has largely been limited to oligomers having a limited number of repeating units due to the difficulties associated with the step-by-step addition of individual monomers to achieve high molecular weights. Here we report the copolymers of α-hydroxy acids, poly(phenyllactic-co-lactic acid) (PcL) built via the cross-convergent method from four dyads of monomers as constituent units. Our proposed method allows scalable synthesis of sequence-defined PcL in a minimal number of coupling steps from reagents in stoichiometric amounts. Digital information can be stored in an aperiodic sequence of PcL, which can be fully retrieved as binary code by mass spectrometry sequencing. The information storage density (bit/Da) of PcL is 50% higher than DNA, and the storage capacity of PcL can also be increased by adjusting the molecular weight (~38 kDa).