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Cross-linking poly(glycidyl methacrylate) microparticles with redox-responsive bis(5-amino-l,3,4-thiadiazol-2-yl) disulfide moieties yield redox-active particles (RAPs) capable of electrochemical energy storage via a reversible 2-electron reduction of the disulfide bond. The resulting RAPs show improved electrochemical reversibility compared to a small-molecule disulfide analogue in solution, attributed to spatial confinement of the polymer-grafted disulfides in the particle. Galvanostatic cycling was used to investigate the impact of electrolyte selection on stability and specific capacity. A dimethyl sulfoxide/magnesium triflate electrolyte was ultimately selected for its favorable electrochemical reversibility and specific capacity. Additionally, the specific capacity showed a strong dependence on particle size where smaller particles yielded higher specific capacity. Overall, these experiments offer a promising direction in designing synthetically facile and electrochemically stable materials for organosulfur-based multielectron energy storage coupled with beyond Li ion systems such as Mg.

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Cross-linked polymer electrolytes containing structurally dynamic disulfide bonds have been synthesized to investigate their combined ion transport and adhesive properties. Dynamic network polymers of varying cross-link densities are synthesized via thiol oxidation of a bisthiol monomer, 2,2'-(ethylenedioxy)diethanethiol, and tetrathiol cross-linker, pentaerythritol tetrakis(3-mercaptopropionate). At optimal loading of lithium bis(trifluoromethane-sulfonyl-imide) (LiTFSI) salt, the ionic conductivities (σ) at 90 °C are about 1 × 10

We investigate the use of in situ enzyme degassing to facilitate the open-to-air reversible addition–fragmentation chain transfer (RAFT) polymerization of hydroxyethyl acrylate (HEA) in a wide range of complex aqueous solvents, including, beer, wine, liquor, and fermentation broth. This enzyme-assisted polymerization procedure is impressively robust, and poly(HEA) was attained with good control over molecular weight and a narrow dispersity in nearly all of the solvents tested. Kinetics experiments on HEA polymerization in whisky and spectroscopic analysis of the purified polymers suggest high end-group fidelity, as does the successful chain extension of a poly(HEA) macro chain transfer agent with narrow dispersity. These results suggest enzyme-assisted RAFT may be a powerful and underutilized tool for high-throughput screening and materials discovery and may simplify the synthesis of well-defined polymers in complex conditions.

Directed self-assembly of a metallosupramolecular polymer is achieved at the interface between two polymer films by simple melt pressing. Blends of a 2,6-bis(N-methylbenzimidazolyl)pyridine (MeBip) side-chain functionalized polystyrene in a polystyrene matrix and Zn(NTf2)2 in a poly(methyl methacrylate) matrix were pressed together above the Tg of the matrix polymers resulting in diffusion of the components and subsequent self-assembly of the metallosupramolecular polymer at the polymer–polymer interface. The formation of the metallosupramolecular polymer was monitored by spectroscopy and microscopy and it was found that the interfacial self-assembly occurs at the processing temperatures (ca. 210 °C) within 5 min. It was further shown that this materials system resulted in robust films that exhibited a new emergent property, namely, phosphorescence, which is not exhibited by any of the individual components nor the metallosupramolecular polymer itself.

Structurally dynamic polydisulfide networks that inherently exhibit both shape-memory and healable properties have been synthesized. These materials are semicrystalline, covalently cross-linked network polymers and as such exhibit thermal shape-memory properties. Upon heating above its melting temperature (Tm) films of the material can be deformed by a force. Subsequent cooling and removal of the force result in the material being “fixed” in this strained temporary shape through a combination of crystallinity and covalent cross-links until it is exposed to temperatures above the Tm at which point it recovers to its remembered processed shape. The incorporation of disulfide bonds, which become dynamic/reversible upon exposure to light or elevated temperatures, into these networks results in them being structurally dynamic upon exposure to the appropriate stimulus. Thus, by activating this disulfide exchange, the network reorganizes, and the material can flow and exhibit healable properties. Furthermore, ex...

Poly[n]catenanes are mechanically interlocked polymers consisting of interlocking ring molecules. Over the years, researchers have speculated that the permanent topological interactions within the ...

We show that functionalization of the surface of cellulose nanocrystals (CNCs) with either carboxylic acid (CNC–CO2H) or amine (CNC–NH2) moieties renders the CNCs pH-responsive. At low pH, where the amine groups are protonated, CNC–NH2 forms aqueous dispersions in water on account of electrostatic repulsions of the ammonium moieties inhibiting aggregation. However, a transition to hydrogels is observed at higher pH where the CNC–NH2 are neutral and the attractive forces based on hydrogen bonding dominate. The opposite behavior is observed for CNC–CO2H, which are dispersible at high pH and form gels in an acidic environment. We further show that these pH-responsive CNCs can be incorporated into a poly(vinyl acetate) matrix to yield mechanically adaptive pH-responsive nanocomposite films.