Out of equilibrium operation of chemical reaction networks (CRNs) enables artificial materials to autonomously respond to their environment by activation and deactivation of intermolecular interactions. Generally, their activation can be driven by various chemical conversions, yet their deactivation to non-interacting building blocks remains largely limited to hydrolysis and internal pH change. To achieve control over deactivation, we present a new, modular CRN that enables reversible formation of positive charges on a tertiary amine substrate, which are removed using nucleophilic signals that control the deactivation kinetics. The modular nature of the CRN enables incorporation in diverse polymer materials, leading to a temporally programmed transition from collapsed and hydrophobic to solvated, hydrophilic polymer chains by controlling polymer-solvent interactions. Depending on the layout of the CRN, we can create stimuli-responsive or autonomously responding materials. This concept will not only offer new opportunities in molecular cargo delivery but also pave the way for next-generation interactive materials.

First report on the sequential, visible light-initiated, single unit monomer insertion (SUMI) of N,N-dimethylacrylamide (DMAm) into the reversible addition fragmentation chain transfer (RAFT) agent, 4-((((2-carboxyethyl)thio)carbonothioyl)thio)-4-cyanopentanoic acid (CTA ), in aqueous solution is provided. The specificity for SUMI over formation of higher oligomers and/or RAFT agent-derived by-products is higher for longer irradiation wavelengths. Red light provides the cleanest product (selective SUMI), showing a linear pseudo-first order kinetic profile to high (>80%) conversion, but also the slowest reaction rate. Blue light provides a relatively rapid reaction, but also gives some by-products (<2%) and the kinetic profile displays a conversion plateau at >65% conversion. Higher specificity with red light is attributed to CTA absorbing at longer wavelengths than the SUMI product, which allows selective excitation of CTA . The use of a higher reaction temperature (65 °C vs ambient) results in a higher reaction rate and a reduction in oligomer formation.

2017)Ultra-fast aqueous polymerisation of acrylamides by high power visible light direct photoactivation RAFT polymerisation. Polymer Chemistry . Permanent WRAP URL: AbstractThe effect of visible LED power (λmax = 402 nm, 451 nm) on kinetics and control of direct photoactivation RAFT polymerisations of acrylamide and dimethylacrylamide are investigated. By increasing power supplied to the LEDs from 6 to 208 W, the polymerisation time required to reach > 85% conversion is reduced from 12 hours to 11 minutes for acrylamide. Similar conversions are shown to be obtainable in 5 minutes for dimethylacrylamide, all without any exogenous photoinitiator or catalyst. This increase in polymerisation rate is attributed to an increase in both photon flux and a coincident increase in polymerisation temperature at higher light intensities. With both 402 nm and 451 nm LEDs exciting the same n → π* electronic transition, little difference in rate of polymerisation is seen between the two light sources. Minimal reduction in polymerisation control is observed at high irradiation intensity for acrylamide, while an increased production of low molecular weight dead chains is observed for dimethylacrylamide. This is shown to be mitigated by controlling the polymerisation temperature to 17°C which caused both a reduction in low molecular weight tailing and an increased polymerisation time.Visible light direct photoactivation RAFT is also shown to have application in the synthesis of ultra-high molecular weight acrylamide polymers (Mn > 1,000,000 g mol -1 ).