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ortho‐Phenylenes are one of the simplest classes of aromatic foldamers, adopting helical geometries because of aromatic stacking interactions. The folding and misfolding ofortho‐phenylenes are slow on the NMR timescale at or below room temperature, allowing detection of folding states using¹H NMR spectroscopy. Herein, anortho‐phenylene hexamer is coupled with a RAFT chain transfer agent (CTA) on each repeat unit. A variety of acrylic monomers are polymerized onto the CTA‐functionalizedortho‐phenylene using PET‐RAFT to yield functionalized star polymers withortho‐phenylene cores. The steric bulk of the acrylate monomer units as well as the chain length of each arm of the star polymer is varied.¹H NMR spectroscopy shows that the folding of theortho‐phenylenes do not vary, providing a robust helical core for star polymer systems.

 

Coronavirus disease 2019 (COVID‐19) has significantly impacted human health, the global economy, and society. Viruses residing on common surfaces represent a potential source of contamination for the general population. Spike binding peptide 1, SBP1 is a 23 amino acid peptide, which has micromolar binding affinity (1.3 μM) towards the spike protein receptor‐binding domain. We hypothesize that if we can covalently immobilize this SBP1 peptide in a covalent crosslinked network system, we can develop a surface that would preferentially bind spike protein and, therefore, which could limit viral spread. A series of covalently crosslinked networks of hydroxy ethyl acrylate (HEA) with different primary chain lengths and crosslinker density was prepared. Later, this network system was functionalized using 2% SBP1 peptide. Our study found that with a shorter chain length and lower crosslinker density, the HEA network system alone could capture almost 80% of the spike protein. We reported that the efficiency could be enhanced almost by 17% with higher crosslinker density.

 

Chemical reactions that mimic the function of ATP hydrolysis in biochemistry are of current interest in nonequilibrium systems chemistry. The formation of transient bonds from these reactions can drive molecular machines or generate materials with time-dependent properties. While the behavior of these systems can be complicated, the underlying chemistry is often simple: they are therefore potentially interesting topics for undergraduate introductory organic chemistry students, combining state-of-the-art advances in systems chemistry with straightforward reactions. Here, a teaching experiment has been developed that explores the transient assembly of benzoic acid derivatives driven by carbodiimide hydration. Working in teams, students examine the formation and decomposition of anhydrides from two benzoic acids using a carbodiimide “fuel”. The students examine classic reaction kinetics of anhydride hydrolysis using two independent methods, NMR and IR spectroscopies. They then explore how the amount of carbodiimide affects the lifetimes of precipitates of benzoic anhydride as a simple example of out-of-equilibrium self-assembly. 

Integration of multiple types of dynamic linkages into one polymer network is challenging and not well understood especially in the design and fabrication of dynamic polymer nanocomposites (DPNs). In this contribution, we present facile methods for synthesizing flexible, healable, conductive, and recyclable thermoresponsive DPNs using three dynamic chemistries playing distinct roles. Dynamic hydrogen bonds account for material flexibility and recycling character. Thiol-Michael exchange accounts for thermoresponsive properties. Diels–Alder reaction leads to covalent bonding between polymer matrix and nanocomposite. Overall, the presence of multiple types of orthogonal dynamic bonds provided a solution to the trade-off between enhanced mechanical performance and material elongation in DPNs. Efficient reinforcement was achieved using <1 wt % multiwalled carbon nanotubes as nanocomposite. Resulting DPNs showed excellent healability with over 3 MPa increase in stress compared to unreinforced materials. Due to multiple responsive dynamic linkages, >90% stress–relaxation was observed with self-healing achieved within 1 h of healing time. Increased mechanical strength, electrical conductivity, and reprocessability were achieved all while maintaining material flexibility and extensibility, hence highlighting the strong promise of these DPNs in the rapidly growing fields of flexible compliant electrodes and strain sensors. 

Photoinduced electron/energy transfer (PET)-reversible addition–fragmentation chain transfer polymerization (RAFT) and conventional photoinitiated RAFT were used to synthesize polymer networks. In this study, two different metal catalysts, namely, tris[2-phenylpyridinato-C2,N]iridium(III) (Ir(ppy)3) and zinc tetraphenylporphyrin (ZnTPP), were selected to generate two different catalytic pathways, one with Ir(ppy)3 proceeding through an energy-transfer pathway and one with ZnTPP proceeding through an electron-transfer pathway. These PET-RAFT systems were contrasted against a conventional photoinitated RAFT process. Mechanically robust materials were generated. Using bulk swelling ratios and degradable cross-linkers, the homogeneity of the networks was evaluated. Especially at high primary chain length and cross-link density, the PET-RAFT systems generated more uniform networks than those made by conventional RAFT, with the electron transfer-based ZnTPP giving superior results to those of Ir(ppy)3. The ability to deactivate radicals either by RAFT exchange or reversible coupling in PET RAFT was proposed as the mechanism that gave better control in PET-RAFT systems.