Zhen-Hua Zhang, Yuyang Chen, Yuesheng Li, Hong Miao
{"title":"A dual-initiating organic frustrated Lewis pair catalyst for living polymerizations of (bio)acrylates to facilitate the synthesis of metal-free multiblock copolymers","authors":"Zhen-Hua Zhang, Yuyang Chen, Yuesheng Li, Hong Miao","doi":"10.1039/d4py01067a","DOIUrl":"https://doi.org/10.1039/d4py01067a","url":null,"abstract":"The development of powerful catalysis or methodologies for the synthesis of fundamentally and technologically important multiblock copolymers is a perpetual task. Dual-initiating Lewis pair (LP) catalysts for living/controlled polymerizations of methyacrylates have demonstrated to be an effective approach to all-acrylic multiblock copolymers. However, the utilization of metal-based Lewis acids (LAs) and complicated Lewis bases (LBs) that typically require laborious syntheses are essential. This contribution reports the first organic dual-initiating Frustrated Lewis pair (FLP) catalysts consisting of tris(2,4-difluorophenyl)borane [B(2,4-F2C6H3)3] LA and commercially available 1,2-bis[(di-tert-butylphosphino)methyl]benzene (DPtBu2) LB, which can mediate efficient and living polymerizations of various (bio)acrylates. Accordingly, all-acrylic multiblock copolymers (up to hepta blocks) with well-defined structures can be readily prepared via sequential monomer addition, thus successfully establishing DPtBu2/B(2,4-F2C6H3)3 FLP as a green/sustainable and user-friendly polymerization catalysis for convenient synthesis of metal-free all-acrylic multiblock copolymers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"49 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832302","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Theoni K. Georgiou, Richard Hoogenboom, Akihiko Kikuchi
{"title":"Introduction to trends in thermoresponsive polymers: from chemistry to applications","authors":"Theoni K. Georgiou, Richard Hoogenboom, Akihiko Kikuchi","doi":"10.1039/d4py90151g","DOIUrl":"https://doi.org/10.1039/d4py90151g","url":null,"abstract":"A graphical abstract is available for this content","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"47 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832386","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Till Meissner, Peter Friedel, Joshua Carroll, Christopher Barner-Kowollik, Jens Gaitzsch
{"title":"Photochemical Action Plots Evidence UV-promoted Radical Ring-Opening Polymerisation of Cyclic Ketene Acetals","authors":"Till Meissner, Peter Friedel, Joshua Carroll, Christopher Barner-Kowollik, Jens Gaitzsch","doi":"10.1039/d4py00847b","DOIUrl":"https://doi.org/10.1039/d4py00847b","url":null,"abstract":"Radical ring-opening polymerisation (RROP) of cyclic ketene acetals (CKAs) is a powerful avenue for the synthesis of biodegradable polyesters with the potential to replace non-decomposable conventional polymers. The radical polymerisation of CKAs is – surprisingly – accelerated by UV light, yet to-date the cause of the acceleration is unknown. We herein demonstrate how highly wavelength-resolved photochemical action plots of the light-induced RROP of 2-methylene-1,3,6-trioxocane (MTC) provide key information for understanding the light-prompted acceleration. We showcase that two wavelengths, 275 and 350 nm, are critical for the acceleration, with the first one facilitating the ring-opening step of the key CKA-intermediate and the second one promoting free radical initiator decay in a wavelength-orthogonal fashion. In contrast to previous studies, we aimed at unravelling the photochemically-driven monomer conversion by performing RROP at room temperature. Computational studies on the MTC radical formed during RROP indicated the cause of the acceleration: A delocalisation of the radical within the ring, which are calculated to be excited by wavelengths close to those identified experimentally. Thus, remarkably, 275 nm light critically accelerates the rate-determining ring-opening step during RROP, suggesting that photons can be used as a traceless reagent in an unexpected fashion to expedite RROPs.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"244 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832300","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Na Wang, Huli Yu, Hai Zhong, Min Duan, Biao Zhao, Jianping Deng
{"title":"Circularly polarized polymeric light-emitting diodes: preparation and properties","authors":"Na Wang, Huli Yu, Hai Zhong, Min Duan, Biao Zhao, Jianping Deng","doi":"10.1039/d4py00939h","DOIUrl":"https://doi.org/10.1039/d4py00939h","url":null,"abstract":"Organic light emitting diodes with circularly polarized luminescence (CPL) properties have drawn extensive attention owing to their significant potentials in 3D displays, spintronics, encrypted data storage, and so forth. Amongst various reported CPL materials, polymer-based chiral emitters have constituted an important class because of their advantages of high thermal stability, good film-forming property, low cost and good solution processability, which are helpful in developing emission-color adjustable, large area and flexible photoelectric devices. In this review, we systematically summarize the state-of-the-art of circularly polarized polymeric light-emitting diodes (CP-PLEDs), in which the different types of polymer-based emitting materials covering chiral conjugated luminescent polymers, achiral conjugated luminescent polymers doped with chiral inducers, and chiral polymer-based metal complexes are introduced. Additionally, the challenges and opportunities for the future development of CP-PLEDs are also discussed. This review article is expected to stimulate more unprecedented achievements of polymer-based CPL emitters as well as the related electroluminescent devices, thus further promoting their future practical applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"48 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832303","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alexander Wong, Cabell B. Eades, Jared Bowman, Cullen Davidson, Brent S. Sumerlin
{"title":"Divergent Photoiniferter Polymerization-Induced Self-Assembly","authors":"Alexander Wong, Cabell B. Eades, Jared Bowman, Cullen Davidson, Brent S. Sumerlin","doi":"10.1039/d4py01323a","DOIUrl":"https://doi.org/10.1039/d4py01323a","url":null,"abstract":"Wavelength-dependent photoreactions present an opportunity to achieve chemoselectivity of functional groups that otherwise demonstrate similar reactivity under traditional thermal conditions. Relying on this concept, we demonstrate that a difunctional iniferter with two thiocarbonylthio groups can be divergently photoactivated to prepare polymeric nanoparticles via polymerization-induced self-assembly (PISA). A hydrophilic poly(oligoethylene glycol methacrylate) macroiniferter was synthesized via selective activation of one thiocarbonylthio moiety with green light. The resulting green-light-active ω-end was then further chain extended with benzyl methacrylate to obtain well-defined nanoparticles by PISA without activation of the blue-light-active α-end iniferter. The obtained nanoparticles could then be used as nanoparticle-iniferters (nanoiniferters) by chain extending from the corona with N,N-dimethylacrylamide via blue-light-mediated photoiniferter polymerization. This approach leverages the wavelength-dependent photolysis of thiocarbonylthio moieties to both synthesize and modify well-defined polymer nanoparticles.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"85 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832384","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xu-tong Guo, Gege Lv, Xinyue Hao, Nanying Ning, Bing Yu, Ming Tian
{"title":"Thermoplastic Polyurethane/Silicone Rubber (TPU/SiR) Thermoplastic Elastomers with Fine Phase Structure and Comfortable Texture based on Polymerization-induced Phase Separation","authors":"Xu-tong Guo, Gege Lv, Xinyue Hao, Nanying Ning, Bing Yu, Ming Tian","doi":"10.1039/d4py01209g","DOIUrl":"https://doi.org/10.1039/d4py01209g","url":null,"abstract":"In this study, the polymerization-induced phase separation (PIPS) method was employed to prepare thermoplastic elastomer (TPE) without using any compatibilizers. The polydimethylsiloxane (PDMS) was dispersed in the Poly-tetramethylene-ether-glycol (PTMG), and underwent phase separation during the polymerization, the TPU/SiR TPEs which were composed of crosslinked silicone rubber (SiR) as the dispersed phase and TPU as the continuous phase. The chemical structure, phase morphology, and mechanical property of the obtained TPE are easily tunable, with an average size of dispersed phase ~0.37 μm and a tensile strength of 13.5 MPa when the pre-polymerization time of TPU is 20 min and the SiR dispersed phase content is 22 wt.%. After repetitive processing, the tensile strength of the recycled material can still reach approximate 80% of the initial value. Moreover, the material exhibits comfortable biological tactile performance, the static and dynamic friction coefficients of this TPE with 33 wt.% SiR are 0.512 and 0.246, respectively, which are much lower than the pure TPU (Us=1.046; Ud=0.544). This method provides a convenient and efficient way to prepare TPE composed of two immiscible phases, and the regulation of phase morphology is very flexible and simple compared with the traditional method.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142825690","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Ruthenium-complex-catalysed de-ammonification polycondensation of aromatic diamines","authors":"Isao Yamaguchi, Takahiro Ooba, Kohei Imoto","doi":"10.1039/d4py01264j","DOIUrl":"https://doi.org/10.1039/d4py01264j","url":null,"abstract":"This study explores a pioneering catalytic reaction to obtain functional polymers and valuable byproducts. Using RuCl<small><sub>2</sub></small>(PPh<small><sub>3</sub></small>)<small><sub>3</sub></small> as a catalyst activates the C–N and N–H bonds in aromatic diamines, when combined with 1,4-butynediol. This activation initiates de-ammonification polycondensation, resulting in aromatic polyamines with a pyrrolyl end group and ammonia as a byproduct. The ammonia generated during the polycondensation process can be captured in cold water. The generation of ammonia during polycondensation was confirmed by UV-vis spectroscopy using the Nessler's reagent method. Subsequently, the aromatic polyamines were further functionalised <em>via</em> polymer reactions with 1,4-butanesultone and butyl isocyanate in the NH group. This yielded products with pendant sodium <em>N</em>-butylsulfonate and <em>N</em>-butylamide groups, respectively. The former exhibited a single-ion conductivity. Potential reaction mechanisms involving Ru-catalysed N–H and C–N bond activation in AD, along with the formation of terminal pyrrolyl groups, were investigated using density functional theorycalculations and <small><sup>2</sup></small>H NMR spectroscopy.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"4 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142815728","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Self-healing and anti-oxidative mucus-inspired hydrogel","authors":"Chunwen Tao, Liyuan Peng, Qiuyun Shao, Kaihui Nan, Ravin Narain, Yangjun Chen","doi":"10.1039/d4py01042f","DOIUrl":"https://doi.org/10.1039/d4py01042f","url":null,"abstract":"Natural mucus-inspired hydrogels have recently garnered significant attention in the fields of drug delivery and tissue engineering. Herein, we successfully prepared mucin-based hydrogels with self-repairing capability and antioxidant activity by employing rational material design principles. By harnessing Bigineli multicomponent reaction and free radical polymerization, antioxidant dihydropyrimidinone (DHPM) and phenylboronic acid (PBA) groups were facilely integrated onto a zwitterionic copolymer (denoted as PMPD). Furthermore, leveraging the abundant glycans present on mucin allowed for dynamic cross-linking through phenylboronic ester bonds with PBA moieties of PMPD to fabricate PM hydrogels. The dynamic nature of phenylboronic ester endowed PM hydrogels with excellent properties such as self-healing, injectable, and self-adaptable. Moreover, owing to the presence of DHPM antioxidant groups along with intrinsic antioxidant activity of mucin, PM hydrogels showed exceptional efficacy in scavenging free radicals. Additionally, PM hydrogel, which was prepared using natural mucin biopolymer and PMPD copolymer mimicking cell membrane structure, showed favorable cytocompatibility. Therefore, our current study represents a novel design strategy for multifunctional mucus-inspired hydrogels that hold promising potential for biomedical applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142820605","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lewis O'Shaughnessy, Akosua Anane-Adjei, Mariarosa Mazza, Naoto Hori, Pratik Gurnani, Cameron Alexander
{"title":"Synthesis and cell-induced luminescence of post-functionalisable ionisable polyesters from the Passerini 3-component polymerisation","authors":"Lewis O'Shaughnessy, Akosua Anane-Adjei, Mariarosa Mazza, Naoto Hori, Pratik Gurnani, Cameron Alexander","doi":"10.1039/d4py01165a","DOIUrl":"https://doi.org/10.1039/d4py01165a","url":null,"abstract":"Recent developments in polymer synthesis methods allow the preparation of new materials across a wide chemical space and with high atom efficiency. In this work, we developed a strategic approach to the synthesis of a diverse array of novel ionisable polyesters via a modular and iterative synthetic approach. We initially designed a range of diacid monomers and subsequently used the Passerini 3-component reaction as a simple, one-pot step growth polymerisation to build a library of novel, highly functionalised polymers. This library was expanded further by the application of thiol/ene and copper-initiated azide/alkyne click chemistries to introduce further structural diversity into the materials. Selected polymers were found to internalise readily in a model cell line (HEK-293T), and for a subset of these polymers, bright luminescence was observed in the cells upon internalisation, even though neither the cells, nor the polymers, were luminescent on their own at these wavelengths. Our synthetic approach offers a versatile platform for the systematic development and modification of novel macromolecules and for cell-labelling components.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"200 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142815628","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}