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  1. Abstract

    Precisely controlling macromolecular stereochemistry and sequences is a powerful strategy for manipulating polymer properties. Controlled synthetic routes to prepare degradable polyester, polycarbonate, and polyether are of recent interest due to the need for sustainable materials as alternatives to petrochemical-based polyolefins. Enantioselective ring-opening polymerization and ring-opening copolymerization of racemic monomers offer access to stereoregular polymers, specifically enantiopure polymers that form stereocomplexes with improved physicochemical and mechanical properties. Here, we highlight the state-of-the-art of this polymerization chemistry that can produce microstructure-defined polymers. In particular, the structures and performances of various homogeneous enantioselective catalysts are presented. Trends and future challenges of such chemistry are discussed.

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  2. Abstract

    Stereoselective ring-opening polymerization catalysts are used to produce degradable stereoregular poly(lactic acids) with thermal and mechanical properties that are superior to those of atactic polymers. However, the process of discovering highly stereoselective catalysts is still largely empirical. We aim to develop an integrated computational and experimental framework for efficient, predictive catalyst selection and optimization. As a proof of principle, we have developed a Bayesian optimization workflow on a subset of literature results for stereoselective lactide ring-opening polymerization, and using the algorithm, we identify multiple new Al complexes that catalyze either isoselective or heteroselective polymerization. In addition, feature attribution analysis uncovers mechanistically meaningful ligand descriptors, such as percent buried volume (%Vbur) and the highest occupied molecular orbital energy (EHOMO), that can access quantitative and predictive models for catalyst development.

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  3. null (Ed.)
    Abstract Immune checkpoint blockade antibodies have promising clinical applications but suffer from disadvantages such as severe toxicities and moderate patient–response rates. None of the current delivery strategies, including local administration aiming to avoid systemic toxicities, can sustainably supply drugs over the course of weeks; adjustment of drug dose, either to lower systemic toxicities or to augment therapeutic response, is not possible. Herein, we develop an implantable miniaturized device using electrode-embedded optical fibers with both local delivery and measurement capabilities over the course of a few weeks. The combination of local immune checkpoint blockade antibodies delivery via this device with photodynamic therapy elicits a sustained anti-tumor immunity in multiple tumor models. Our device uses tumor impedance measurement for timely presentation of treatment outcomes, and allows modifications to the delivered drugs and their concentrations, rendering this device potentially useful for on-demand delivery of potent immunotherapeutics without exacerbating toxicities. 
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  4. null (Ed.)
    Poly(α-hydroxy acids), as a family of biodegradable polyesters, are valuable materials due to their broad applications in packaging, agriculture, and biomedical engineering. Herein we highlight and explore recent advances of catalysts in controlled ring-opening polymerization of O-carboxyanhydrides towards functionalized poly(α-hydroxy acids), especially metal catalyst-mediated controlled polymerization. Limitations of current polymerization strategies of O-carboxyanhydrides are discussed. 
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  5. Abstract

    Transforming renewable resources into functional and degradable polymers is driven by the ever‐increasing demand to replace unsustainable polyolefins. However, the utility of many degradable homopolymers remains limited due to their inferior properties compared to commodity polyolefins. Therefore, the synthesis of sequence‐defined copolymers from one‐pot monomer mixtures is not only conceptually appealing in chemistry, but also economically attractive by maximizing materials usage and improving polymers’ performances. Among many polymerization strategies, ring‐opening (co)polymerization of cyclic monomers enables efficient access to degradable polymers with high control on molecular weights and molecular weight distributions. Herein, we highlight recent advances in achieving one‐pot, sequence‐controlled polymerizations of cyclic monomer mixtures using a single catalytic system that combines multiple catalytic cycles. The scopes of cyclic monomers, catalysts, and polymerization mechanisms are presented for this type of sequence‐controlled ring‐opening copolymerization.

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  6. null (Ed.)
    Photoredox ring-opening polymerization of O -carboxyanhydrides allows for the synthesis of polyesters with precisely controlled molecular weights, molecular weight distributions, and tacticities. While powerful, obviating the use of precious metal-based photocatalysts would be attractive from the perspective of simplifying the protocol and enabling unexpected reactivity. Herein, we report the Co and Zn catalysts that are activated by external light to mediate efficient ring-opening polymerization of O -carboxyanhydrides, without the use of exogenous precious metal-based photocatalysts. Our methods allow for the synthesis of isotactic polyesters with high molecular weights (>200 kDa) and narrow molecular weight distributions ( M w / M n < 1.1). Mechanistic studies indicate that light activates the oxidative status of Co III intermediate that is generated from the regioselective ring-opening of the O -carboxyanhydride. We also demonstrate that the use of Zn or Hf complexes together with Co can allow for stereoselective photoredox ring-opening polymerizations of multiple racemic O -carboxyanhydrides to synthesize syndiotactic and stereoblock copolymers, which vary widely in their glass transition temperatures. 
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