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Molecular architectures known as bottlebrush polymers provide unique opportunities to tune the structure and properties of soft materials with applications ranging from rubbers to thin films and composites. This review addresses recent developments and future opportunities in the field with an emphasis on materials science enabled by contemporary bottlebrush chemistry. 

<sc>A</sc>bstract We introduce a simple synthetic strategy to selectively degrade bottlebrush networks derived from well‐defined poly(4‐methylcaprolactone) (P4MCL) bottlebrush polymers. Functionalization of the hydroxyl groups present at the terminal ends of P4MCL side chains withα‐lipoic acid resulted in bottlebrush polymers having a range of molecular weights (M_n = 45–2200 kg mol⁻¹) and a tunable number of reactive dithiolane chain ends. These functionalized chain ends act as efficient crosslinkers due to radical ring‐opening of the dithiolane rings under UV light. The resulting redox‐active disulfide crosslinks enable mild electrochemical or chemical degradation of the SS crosslinks to regenerate the starting bottlebrush polymer. P4MCL side chains and the disulfides can be degraded simultaneously using harsher reducing conditions. This combination of bottlebrush architecture with facile disulfide crosslinking presents a versatile platform for preparing highly tunable elastomers that undergo controlled degradation under mild conditions. 

Dynamic nuclear polarization (DNP) can amplify the solid-state nuclear magnetic resonance (NMR) signal by several orders of magnitude. The mechanism of DNP utilizing α,γ- Bisdiphenylene-β-phenylallyl (BDPA) variants as Polarizing Agents (PA) has been the subject of lively discussions on account of their remarkable DNP efficiency with low demand for microwave power. We propose that electron spin clustering of SA-BDPA is responsible for its DNP performance, as revealed by the temperature-dependent shape of the central DNP profile and strong electron-electron (e-e) crosstalk seen by Electron Double Resonance. We demonstrate that a multi-electron spin cluster can be modeled with three coupled spins, where electron J (exchange) coupling between one of the e-e pairs matching the NMR Larmor frequency induces the experimentally observed absorptive central DNP profile, and the electron T1e modulated by temperature and magic angle spinning alters the shape between an absorptive and dispersive feature. Understanding the microscopic origin is key to designing new PAs to harness the microwave power-efficient DNP effect observed with BDPA variants. 

ABSTRACT The introduction of degradable units into the backbone of commodity vinyl polymers represents a major opportunity to address the societal challenge of plastic waste and polymer recycling. Previously, we reported the facile copolymerization ofα‐lipoic acid derivatives containing 1,2‐dithiolane rings with vinyl monomers leading to the incorporation of degradable S–S disulfide bonds along the backbone at relatively high dithiolane monomer feed ratios. To further enhance the recyclability of these systems, here we describe a facile and user‐friendly strategy for backbone degradation at significantly lower dithiolane loading levels through cleavage of both SS and SC backbone units. Copolymers ofn‐butyl acrylate (nBA) or styrene (St) with small amounts of eitherα‐lipoic acid (LA) or ethyl lipoate (ELp) dissolved in DMF were observed to undergo efficient degradation when heated at 100°C under air. For example, at only 5 mol% ELp, a high molecular weight poly(ELp‐co‐nBA) (M_n = 62 kg mol⁻¹) degraded to low molecular weight oligomers (M_n = 3.2 kg mol⁻¹) by simple heating in DMF. In contrast, extended heating of either poly(nBA) or poly(St) homopolymers under the same conditions did not lead to any change in molecular weight or cleavage of the C–C backbone. This novel approach allows for the effective degradation of vinyl‐based polymers with negligible impact on properties and performance due to the low levels of dithiolane incorporation.