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1. Sequential and one-pot post-polymerization modification reactions of thiolactone-containing polymer brushes

   https://doi.org/10.1039/C9PY01123D  

   Reese, Cassandra M.; Thompson, Brittany J.; Logan, Phillip K.; Stafford, Christopher M.; Blanton, Michael; Patton, Derek L. (January 2019, Polymer Chemistry)

   Thiolactone chemistry has garnered significant attention as a powerful post-polymerization modification (PPM) route to mutlifunctional polymeric materials. Here, we apply this versatile chemistry to the fabrication of ultrathin, multifunctional polymer surfaces via aminolysis and thiol-mediated double modifications of thiolactone-containing polymer brushes. Polymer brush surfaces were synthesized via microwave-assisted surface-initiated polymerization of dl -homocysteine thiolactone acrylamide. Aminolysis and thiol-Michael double modifications of the thiolactone-functional brush were explored using both sequential and one-pot reactions with bromobenzyl amine and 1 H ,1 H -perfluoro- N -decyl acrylate. X-ray photoelectron spectroscopy and argon gas cluster ion sputter depth profiling enabled quantitative comparison of the sequential and one-pot PPM routes with regard to conversion and spatial distribution of functional groups immobilized throughout thickness of the brush. While one-pot conditions proved to be more effective in immobilizing the amine and acrylate within the brush, the sequential reaction enabled the fabrication of multifunctional, micropatterned brush surfaces using reactive microcontact printing. 

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2. Development of Multifunctional Cathode Binder via Inverse Vulcanization for Lithium–Sulfur Battery with Enhanced Capacity Retention

   https://doi.org/10.1021/acs.jpcc.3c02096  

   Jeong, Jisoo; Kyu, Thein (June 2023, The Journal of Physical Chemistry C)

   Vinyl-benzaldehyde (VB) monomers containing four functional groups were newly synthesized using the Williamson ether synthesis method. The two aldehyde groups of the synthesized monomers were able to react with amine-terminated macromonomers to form flexible networks. In addition, the two vinyl groups were found to be capable of inverse vulcanization with sulfur by conducting qualitative chemical analysis. The lithium−sulfur battery prepared using the VB-based cathode binder achieved high specific capacity with excellent capacity retention compared to conventional sulfur batteries, demonstrating the potential of the new binder. 

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3. Supramolecular bottlebrush copolymers from crown-ether functionalized poly( p -phenylenevinylene)s

   https://doi.org/10.1039/D4PY01225A  

   Keer, Anahita; Mann, Arielle; Wang, Chengyuan; Weck, Marcus (February 2025, Polymer Chemistry)

   Crown-ether functionalized poly(p-phenylenevinylene) (red) and cationic dibenzyl amine chain-end functionalized poly(styrene) (blue) were synthesized and assembled into optically active, pH responsive, and semi-crystalline bottlebrush copolymers. 

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4. Post-polymerization modification of styrene–maleic anhydride copolymer brushes

   https://doi.org/10.1039/c7py01659j  

   Guo, Wei; Xiong, Li; Reese, Cassandra M.; Amato, Douglas V.; Thompson, Brittany J.; Logan, Phillip K.; Patton, Derek L. (January 2017, Polymer Chemistry)

   Post-polymerization modification (PPM) has been broadly employed to achieve functional polymer brush surfaces via immobilization of functional moieties on the brush using efficient organic tranformations. Here, we demonstrate the amine-anhydride reaction as a modular PPM route to functional brush surfaces using poly(styrene–maleic anhydride) (pSMA) copolymer brushes as a platform. The amine-anhydride reaction on pSMA surfaces proceeds to high conversions, with rapid kinetics, under ambient reaction conditions, and exploits a readily available library of functional amines. Using cystamine as a modifier, a convenient route to thiol-functionalized brushes was developed that enables sequential PPM modifications with a large library of alkenes using both base-catalyzed thiol-Michael and radical-mediated thiol–ene reactions. The high fidelity PPM reactions were demonstrated via the development of multifunctional, micropatterned brush surfaces. 

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5. Bipolar Organic Cathodes for Stable and Sustainable Na‐Ion and Rechargeable Al Batteries

   https://doi.org/10.1002/batt.202400325  

   Youngsam_Kim, Eric; Vi‐khanh_Ta, Kaitlyn; Chen, Fu; Yang, Zhenzhen; Yu, Yun; Luo, Chao (July 2024, Batteries & Supercaps)

   Abstract Bipolar organic materials have emerged as promising cathode materials for rechargeable batteries because of their high voltage and high capacity. However, they suffer from poor cyclic stability and slow reaction kinetics. In this work, we designed and synthesized two bipolar organic cathode materials, containing carbonyl (n‐type) and amine (p‐type) functional groups, as well as extended conjugation structures, for Na‐ion batteries (NIBs) and rechargeable aluminum batteries (RABs). As universal electrode materials, bipolar organic materials exhibited exceptional electrochemical performance in terms of high capacity, high voltage, long cycle life, and fast rate capability. The extended conjugation structures in backbones of the bipolar organic materials facilitate the π–π stacking with graphene, playing a critical role in the high performance. Furthermore, the formation of a stable and robust NaF‐rich cathode electrolyte interphase was shown to stabilize the bipolar organic cathode in NIBs. Electrochemical kinetic measurements reveal that both functional groups undergo reversible redox reactions. Specifically, the electron transfer rate constant of the p‐type amine group is one order of magnitude higher than that of the n‐type carbonyl group. These results highlight the efficacy of developing bipolar organic materials for achieving high‐performance organic cathode in NIBs and RABs. 

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