Engineering reaction microenvironment in immobilized molecular catalysts is essential for programmable catalytic performance. Herein, we introduce a molecular strategy to regulate the reaction microenvironment based on cross-linking structure of polymer-bound catalysts. A series of polymer-bound tris(2,2′-bipyridine)Ru(II) complexes are synthesized by systematically varying the number and position of covalent anchor points between the Ru complex and polymer chains. Photoluminescence lifetime and absolute quantum yield measurements reveal that increasing the covalent anchors progressively suppresses structural mobility of the Ru core. Stern-Volmer quenching analysis shows that excessive local cross-linking lowers diffusional accessibility of dissolved O2 to the Ru complex due to sterically hindered polymer network. We elucidated that photocatalytic kinetics in a 1O2-mediated anthracene oxidation are determined by both the catalyst mobility and molecular accessibility, which correlates with energy transfer probability from a photoexcited Ru complex to dissolved O2. These findings identify the local cross-linking structure surrounding the active site as a molecular design parameter for engineering the reaction microenvironment in immobilized catalysis.
{"title":"Local Cross-Linking Structure Regulates Active Site Mobility and Molecular Accessibility in Polymer-Bound Photocatalysts","authors":"Hikaru Matsumoto,Masanori Nagao,Yoshiko Miura","doi":"10.1039/d6py00862c","DOIUrl":"https://doi.org/10.1039/d6py00862c","url":null,"abstract":"Engineering reaction microenvironment in immobilized molecular catalysts is essential for programmable catalytic performance. Herein, we introduce a molecular strategy to regulate the reaction microenvironment based on cross-linking structure of polymer-bound catalysts. A series of polymer-bound tris(2,2′-bipyridine)Ru(II) complexes are synthesized by systematically varying the number and position of covalent anchor points between the Ru complex and polymer chains. Photoluminescence lifetime and absolute quantum yield measurements reveal that increasing the covalent anchors progressively suppresses structural mobility of the Ru core. Stern-Volmer quenching analysis shows that excessive local cross-linking lowers diffusional accessibility of dissolved O2 to the Ru complex due to sterically hindered polymer network. We elucidated that photocatalytic kinetics in a 1O2-mediated anthracene oxidation are determined by both the catalyst mobility and molecular accessibility, which correlates with energy transfer probability from a photoexcited Ru complex to dissolved O2. These findings identify the local cross-linking structure surrounding the active site as a molecular design parameter for engineering the reaction microenvironment in immobilized catalysis.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"57 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218278","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}
William Ramos,Nicholas M. Legaux,Brandon M. Hosford,Hanlin M. Wang,Elizabeth A. Murphy,Alicia C. Huggett,Frank A. Leibfarth,Jessica R. Lamb
Tacticity can have profound effects on the physical properties of polymers, such as self-assembly of block copolymers (BCPs). Despite its promise, previous reports on changing tacticity of BCPs have primarily focused on changing a single block or comparing fully isotactic to fully atactic copolymers. Herein, we report a platform to easily access fully atactic, fully isotactic, and mixed tacticity poly(vinyl ether)-block-poly(thiirane) BCPs. Isotacticity was independently accessed via stereoselective polymerization of vinyl ethers and by using enantiopure thiirane monomers, respectively. Thermal analyses of these materials were performed and semi-crystallinity was observed in aryl-containing isotactic blocks. For BCPs with alkyl side chains or atactic aryl side chains, fractionation on the basis of composition was performed to accelerate self-assembly studies. These fractionated BCPs were characterized via small-angle X-ray scattering (SAXS), where we observed hexagonally-packed cylinder or lamellar morphologies for some fractions. The development of this framework of selective tacticity modulation opens up facile access to diverse BCPs with varying thermal, solution-state, and bulk properties.
{"title":"Accessing block copolymers with independently modulated tacticities using sequential cationic–anionic polymerization of vinyl ethers and thiiranes","authors":"William Ramos,Nicholas M. Legaux,Brandon M. Hosford,Hanlin M. Wang,Elizabeth A. Murphy,Alicia C. Huggett,Frank A. Leibfarth,Jessica R. Lamb","doi":"10.1039/d6py00788k","DOIUrl":"https://doi.org/10.1039/d6py00788k","url":null,"abstract":"Tacticity can have profound effects on the physical properties of polymers, such as self-assembly of block copolymers (BCPs). Despite its promise, previous reports on changing tacticity of BCPs have primarily focused on changing a single block or comparing fully isotactic to fully atactic copolymers. Herein, we report a platform to easily access fully atactic, fully isotactic, and mixed tacticity poly(vinyl ether)-block-poly(thiirane) BCPs. Isotacticity was independently accessed via stereoselective polymerization of vinyl ethers and by using enantiopure thiirane monomers, respectively. Thermal analyses of these materials were performed and semi-crystallinity was observed in aryl-containing isotactic blocks. For BCPs with alkyl side chains or atactic aryl side chains, fractionation on the basis of composition was performed to accelerate self-assembly studies. These fractionated BCPs were characterized via small-angle X-ray scattering (SAXS), where we observed hexagonally-packed cylinder or lamellar morphologies for some fractions. The development of this framework of selective tacticity modulation opens up facile access to diverse BCPs with varying thermal, solution-state, and bulk properties.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218276","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}
Jiahe Wang,Arkadios Marathianos,Minen Cao,Xu Liu,Theoni K Georgiou
Thermoresponsive polymers based on poly(ethylene glycol) (PEG) have attracted significant attention in various applications, especially in biomedical fields, because of their excellent biocompatibility and high tunability which can be controlled by varying the molecular mass (MM), architecture, and monomer composition. In this study, the monomers oligo(ethylene glycol) methyl ether methacrylate (OEGMA300, average MM = 300 g mol-1) and di(ethylene glycol) methyl ether methacrylate (DEGMA) were selected. OEGMA300, with its longer EG side chains, is more hydrophilic than the relatively hydrophobic DEGMA. Linear copolymers based on these monomers have been investigated, whereas star-shaped polymers have not, and more importantly, a direct comparison of linear and star-shaped polymers as thermogels has not previously been reported. Thus, in this investigation, a series of linear and star polymers composed of OEGMA300 and DEGMA were synthesised via group transfer polymerisation (GTP) with the concentration of the OEGMA300 content ranging from 65 wt% to 35 wt %. Star polymers of different architectures and monomer sequences were synthesised, and their thermal behaviour was investigated. Gel permeation chromatography (GPC) and proton nuclear magnetic resonance (NMR) spectroscopy were used to determine the MMs and compositions of the obtained polymers. Two important transition temperatures, cloud point temperature (Tcp) and gelation temperature (Tgel), were identified through characterisation techniques, including turbidimetry, dynamic light scattering (DLS), visual tests, and rheology. The star polymer which exhibited the best gelation behaviour was the heteroarm star containing 35 wt% OEGMA300 and 65 wt% DEGMA. VT-1H NMR was also performed to investigate the dual-transition behaviour observed in DEGMA-first diblock linear polymers.
{"title":"Thermoresponsive Behaviour of PEG-Based Methacrylate Polymers: Influence of Linear and Star Architectures","authors":"Jiahe Wang,Arkadios Marathianos,Minen Cao,Xu Liu,Theoni K Georgiou","doi":"10.1039/d6py00821f","DOIUrl":"https://doi.org/10.1039/d6py00821f","url":null,"abstract":"Thermoresponsive polymers based on poly(ethylene glycol) (PEG) have attracted significant attention in various applications, especially in biomedical fields, because of their excellent biocompatibility and high tunability which can be controlled by varying the molecular mass (MM), architecture, and monomer composition. In this study, the monomers oligo(ethylene glycol) methyl ether methacrylate (OEGMA300, average MM = 300 g mol-1) and di(ethylene glycol) methyl ether methacrylate (DEGMA) were selected. OEGMA300, with its longer EG side chains, is more hydrophilic than the relatively hydrophobic DEGMA. Linear copolymers based on these monomers have been investigated, whereas star-shaped polymers have not, and more importantly, a direct comparison of linear and star-shaped polymers as thermogels has not previously been reported. Thus, in this investigation, a series of linear and star polymers composed of OEGMA300 and DEGMA were synthesised via group transfer polymerisation (GTP) with the concentration of the OEGMA300 content ranging from 65 wt% to 35 wt %. Star polymers of different architectures and monomer sequences were synthesised, and their thermal behaviour was investigated. Gel permeation chromatography (GPC) and proton nuclear magnetic resonance (NMR) spectroscopy were used to determine the MMs and compositions of the obtained polymers. Two important transition temperatures, cloud point temperature (Tcp) and gelation temperature (Tgel), were identified through characterisation techniques, including turbidimetry, dynamic light scattering (DLS), visual tests, and rheology. The star polymer which exhibited the best gelation behaviour was the heteroarm star containing 35 wt% OEGMA300 and 65 wt% DEGMA. VT-1H NMR was also performed to investigate the dual-transition behaviour observed in DEGMA-first diblock linear polymers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"31 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173148","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}
Zhenjie Ni,Chenzhan Wang,Congze Xu,Anxin Zhao,Linyi Xue,Hongbin Sun,Tongtong Zhao,Hanlin Wang,Wenping Hu
Cyano groups are compact, polar, and electron-withdrawing moieties that have been extensively utilised to tune the physicochemical properties of pharmaceutical molecules. Moreover, they are inherent acceptors of electrons and hydrogen bonds. Thus, they are expected to exert an unprecedented influence on the characteristics of organic mixed ionic-electronic conductors (OMIECs). However, the regioisomeric effects of cyano substitution on the electron density distribution, swelling, and performance within OMIECs remain insufficiently understood. In this study, we exchange the substituent position of cyano groups in donor-acceptor OMIECs and investigate the structure-mixed conduction characteristics. As a result, increase in the product of μC* was determined to be approximately 8-fold and 22-fold increases for cyanated 2,2'-Bithiophene(2T) and 2,2'-(1,2-ethenediyl)bis-Thiophene(TVT)-based OMIECs. This comprehensive improvement is ascribed to the promoted hydrophilicity and electron-accepting capability of the comonomers. Electrostatic potential calculations reveal a more uniform distribution of negatively charged carriers along the backbone following comonomer substitution, suggesting a higher electrochemical reduction capacity upon its interaction with Na+ ions. Moreover, in situ UV–vis–NIR spectroscopy confirms charged-state formation, while grazing-incidence wide-angle X-ray scattering reveals expanded π–π stacking coherence lengths following doping. These findings establish cyano-substituent regiochemistry as a decisive parameter to boost ionic-electronic transport in n-type OMIECs.
{"title":"Modulating the Performance of N-Type Organic Conductors through Cyano Substituent Regiochemistry","authors":"Zhenjie Ni,Chenzhan Wang,Congze Xu,Anxin Zhao,Linyi Xue,Hongbin Sun,Tongtong Zhao,Hanlin Wang,Wenping Hu","doi":"10.1039/d6py00836d","DOIUrl":"https://doi.org/10.1039/d6py00836d","url":null,"abstract":"Cyano groups are compact, polar, and electron-withdrawing moieties that have been extensively utilised to tune the physicochemical properties of pharmaceutical molecules. Moreover, they are inherent acceptors of electrons and hydrogen bonds. Thus, they are expected to exert an unprecedented influence on the characteristics of organic mixed ionic-electronic conductors (OMIECs). However, the regioisomeric effects of cyano substitution on the electron density distribution, swelling, and performance within OMIECs remain insufficiently understood. In this study, we exchange the substituent position of cyano groups in donor-acceptor OMIECs and investigate the structure-mixed conduction characteristics. As a result, increase in the product of μC* was determined to be approximately 8-fold and 22-fold increases for cyanated 2,2'-Bithiophene(2T) and 2,2'-(1,2-ethenediyl)bis-Thiophene(TVT)-based OMIECs. This comprehensive improvement is ascribed to the promoted hydrophilicity and electron-accepting capability of the comonomers. Electrostatic potential calculations reveal a more uniform distribution of negatively charged carriers along the backbone following comonomer substitution, suggesting a higher electrochemical reduction capacity upon its interaction with Na+ ions. Moreover, in situ UV–vis–NIR spectroscopy confirms charged-state formation, while grazing-incidence wide-angle X-ray scattering reveals expanded π–π stacking coherence lengths following doping. These findings establish cyano-substituent regiochemistry as a decisive parameter to boost ionic-electronic transport in n-type OMIECs.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"10 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173145","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}
Crosslinked anion exchange membranes (NMPDx-NMPy-cQPVB/PVA) are prepared by grafting N-methylpiperidinone and N-methylpiperidine onto poly(4-vinylbenzyl chloride) (PVB) via a Menshutkin reaction, followed by an acid-catalyzed ketal crosslinking with poly(vinyl alcohol) (PVA). The combination of rigid PVB and flexible PVA provides balanced mechanical strength and flexibility, while the ether-free backbone and quaternized N-methylpiperidinium cations ensure promising alkaline stability. The ketal-based crosslinking preserves cation grafting sites, enabling a high degree of functionalization and comparable ionic conductivity. The optimized NMPD20-NMP40-cQPVB/PVA membrane exhibits an in-plane swelling ratio of 3.8% and ionic conductivity of 126.2 mS cm−1 at 80 °C, wet-tensile strength of 10.7 MPa, and elongation at break of 16.6% at room temperature. After 30 days in 1 M KOH at 80 °C, it retains 84.3% of its mass and 91.2% of its conductivity. In water electrolysis operation, the membrane achieves 1.85 A cm−2 at 2.0 V and 80 °C, with a voltage decay rate of 0.125 mV h−1 over 80 h at 1.0 A cm−2.
通过Menshutkin反应将n -甲基哌啶酮和n -甲基哌啶接枝到聚（4-乙烯基氯化苄）（PVB）上，然后与聚乙烯醇（PVA）进行酸催化的酮交联，制备了交联阴离子交换膜（NMPDx-NMPy-cQPVB/PVA）。刚性PVB和柔性PVA的结合提供了平衡的机械强度和柔韧性，而无醚骨架和季铵盐化的n -甲基哌啶离子确保了良好的碱性稳定性。基于金酮的交联保留了阳离子接枝位点，实现了高度的功能化和相当的离子电导率。优化后的NMPD20-NMP40-cQPVB/PVA膜在80℃时的面内膨胀率为3.8%，离子电导率为126.2 mS cm−1，室温湿拉伸强度为10.7 MPa，断裂伸长率为16.6%。在80°C、1 M KOH中浸泡30天后，其质量保持84.3%，电导率保持91.2%。在电解过程中，该膜在2.0 V和80℃条件下的电压衰减率为1.85 A cm−2，在1.0 A cm−2条件下，80 h内的电压衰减率为0.125 mV h−1。
{"title":"Stable ketal-crosslinked anion exchange membranes combining ether-free backbones, piperidinium cations, and rigid–flexible networks","authors":"Minhao Wang,Cuiwen Deng,Yi Hu,Quan Yang,Xinjie Zhang,Yangrun Cao,Yufan Zheng,Haiting Zhou,Yuanlu Deng,Yifei Long,Guozhi Fan,Yi Liu,Juanjuan Han","doi":"10.1039/d6py00668j","DOIUrl":"https://doi.org/10.1039/d6py00668j","url":null,"abstract":"Crosslinked anion exchange membranes (NMPDx-NMPy-cQPVB/PVA) are prepared by grafting N-methylpiperidinone and N-methylpiperidine onto poly(4-vinylbenzyl chloride) (PVB) via a Menshutkin reaction, followed by an acid-catalyzed ketal crosslinking with poly(vinyl alcohol) (PVA). The combination of rigid PVB and flexible PVA provides balanced mechanical strength and flexibility, while the ether-free backbone and quaternized N-methylpiperidinium cations ensure promising alkaline stability. The ketal-based crosslinking preserves cation grafting sites, enabling a high degree of functionalization and comparable ionic conductivity. The optimized NMPD20-NMP40-cQPVB/PVA membrane exhibits an in-plane swelling ratio of 3.8% and ionic conductivity of 126.2 mS cm−1 at 80 °C, wet-tensile strength of 10.7 MPa, and elongation at break of 16.6% at room temperature. After 30 days in 1 M KOH at 80 °C, it retains 84.3% of its mass and 91.2% of its conductivity. In water electrolysis operation, the membrane achieves 1.85 A cm−2 at 2.0 V and 80 °C, with a voltage decay rate of 0.125 mV h−1 over 80 h at 1.0 A cm−2.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"30 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173149","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}
Benjamin R. Nelson,Kristi S Anseth,Christopher N. Bowman
1,2-Dithiolanes occupy a unique position as monomers that facilitate multiple materials solutions at the intersection of biochemistry, photochemistry, and (bio)materials science. Unlike many cyclic monomers where the versatility of substituents underlies their utility, dithiolanes are defined by the intrinsic variability in the reactive pathways of the ring itself, including its capacity to homopolymerize through numerous pathways or copolymerize with various other categories of monomers. The ring strain in five-membered cyclic disulfides renders it inherently polymerizable, dynamic, and photoreactive. Depending on conditions, dithiolanes are capable of polymerization via radical-mediated, ionic, photoinduced, thermal, and other mechanisms, all of which directly result in dynamic polydisulfides. This perspective describes the history and development of dithiolane polymerizations and highlights current and potential applications of the resulting materials, especially in the development and implementation of covalent adaptable networks.
{"title":"1,2-Dithiolanes in photodynamic linear and network polymers: current applications and future directions","authors":"Benjamin R. Nelson,Kristi S Anseth,Christopher N. Bowman","doi":"10.1039/d6py00798h","DOIUrl":"https://doi.org/10.1039/d6py00798h","url":null,"abstract":"1,2-Dithiolanes occupy a unique position as monomers that facilitate multiple materials solutions at the intersection of biochemistry, photochemistry, and (bio)materials science. Unlike many cyclic monomers where the versatility of substituents underlies their utility, dithiolanes are defined by the intrinsic variability in the reactive pathways of the ring itself, including its capacity to homopolymerize through numerous pathways or copolymerize with various other categories of monomers. The ring strain in five-membered cyclic disulfides renders it inherently polymerizable, dynamic, and photoreactive. Depending on conditions, dithiolanes are capable of polymerization via radical-mediated, ionic, photoinduced, thermal, and other mechanisms, all of which directly result in dynamic polydisulfides. This perspective describes the history and development of dithiolane polymerizations and highlights current and potential applications of the resulting materials, especially in the development and implementation of covalent adaptable networks.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"10 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173146","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}
Raul S Ramos,Fernando Munoz Alba,Kavish Saini,Alicia Loya,Carlos Cabrera-Martinez,Sreeprasad T Sreenivasan,M. Carmen Ruiz Delgado,Rocio Ponce Ortiz,Robert Mark Pankow
Stimuli-responsive polymers offer dynamic functionality via molecular reporters that provide optical, electronic, or electrochemical signaling following the application of optical, chemical, mechanical, or thermal stimuli. Spiropyran is a colorless compound capable of isomerizing to the vibrantly colored merocyanine, and it has been incorporated into non-conjugated polymer scaffolds for photochromic and mechanochromic applications. However, stimuli-responsive main-chain spiropyran copolymers with π-conjugated comonomers remain relatively undeveloped, and it is unclear how the conjugated comonomer identity and functionalization of spiropyran influence its isomerization to merocyanine. Here, the electrochemical and acid-induced isomerization of main-chain spiropyran copolymers are systematically probed where the identity of the comonomer (fluorene or carbazole) and the functionalization of spiropyran are altered to develop key structure-function relationships and mechanistic insight. The polymers PF-SP, PF-SPn, PCBz-SP, and PCBz-SPn were synthesized via Suzuki polymerization and fully characterized via NMR, GPC, TGA, DSC, and AFM. DFT and TD-DFT calculations were performed using model compounds to assess the electronic structure and changes in optical properties following oxidation and isomerization. The polymers were incorporated into electrochromic devices to evaluate the electrochemical isomerization to merocyanine. It is found that the identity of the comonomer plays a central role in achieving optimal ECD performance metrics (optical contrast, switching times, and coloration efficiency), and that the polymer remains in the merocyanine form following its initial isomerization. Acid-induced isomerization yields unique optical absorption spectra with distinct structure-property relationships in comparison to electrochemical isomerization.
{"title":"Disentangling the Electrochromic and Acidochromic Optical Switching in Multi-Stimuli-Responsive Spiropyran Copolymers","authors":"Raul S Ramos,Fernando Munoz Alba,Kavish Saini,Alicia Loya,Carlos Cabrera-Martinez,Sreeprasad T Sreenivasan,M. Carmen Ruiz Delgado,Rocio Ponce Ortiz,Robert Mark Pankow","doi":"10.1039/d6py00735j","DOIUrl":"https://doi.org/10.1039/d6py00735j","url":null,"abstract":"Stimuli-responsive polymers offer dynamic functionality via molecular reporters that provide optical, electronic, or electrochemical signaling following the application of optical, chemical, mechanical, or thermal stimuli. Spiropyran is a colorless compound capable of isomerizing to the vibrantly colored merocyanine, and it has been incorporated into non-conjugated polymer scaffolds for photochromic and mechanochromic applications. However, stimuli-responsive main-chain spiropyran copolymers with π-conjugated comonomers remain relatively undeveloped, and it is unclear how the conjugated comonomer identity and functionalization of spiropyran influence its isomerization to merocyanine. Here, the electrochemical and acid-induced isomerization of main-chain spiropyran copolymers are systematically probed where the identity of the comonomer (fluorene or carbazole) and the functionalization of spiropyran are altered to develop key structure-function relationships and mechanistic insight. The polymers PF-SP, PF-SPn, PCBz-SP, and PCBz-SPn were synthesized via Suzuki polymerization and fully characterized via NMR, GPC, TGA, DSC, and AFM. DFT and TD-DFT calculations were performed using model compounds to assess the electronic structure and changes in optical properties following oxidation and isomerization. The polymers were incorporated into electrochromic devices to evaluate the electrochemical isomerization to merocyanine. It is found that the identity of the comonomer plays a central role in achieving optimal ECD performance metrics (optical contrast, switching times, and coloration efficiency), and that the polymer remains in the merocyanine form following its initial isomerization. Acid-induced isomerization yields unique optical absorption spectra with distinct structure-property relationships in comparison to electrochemical isomerization.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"232 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173144","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}
Kristi Anseth,Christopher N. Bowman,Filip E. Du Prez,Tao Xie
{"title":"Introduction to dynamic polymer networks","authors":"Kristi Anseth,Christopher N. Bowman,Filip E. Du Prez,Tao Xie","doi":"10.1039/d6py90113a","DOIUrl":"https://doi.org/10.1039/d6py90113a","url":null,"abstract":"","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"167 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151994","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}
Polyurethane foam represents the predominant form of polyurethane materials and is extensively utilized in applications such as thermal insulation, soundproofing, and vibration damping. Owing to its inherently stable covalently cross-linked network, which severely limits reprocessing and remolding, the recycling and reuse of polyurethane foam have long attracted considerable attention in both academic and industrial communities. This review summarizes recent advancements in polyurethane foam recycling enabled by dynamic covalent chemistry. Key topics include the incorporation of dynamic covalent bonds, the associated changes in material properties, and representative recycling methodologies and products, such as densified films, adhesives, re-foamed foams, and 3D-printable resins. Furthermore, current challenges and future prospects are discussed to provide insights into the high-value recycling of polyurethane foams and the sustainable development of the polyurethane industry.
{"title":"Polyurethane Foam Recycling Based on Dynamic Covalent Chemistry: Strategies and Perspectives","authors":"Jing Wang,Yang You","doi":"10.1039/d6py00698a","DOIUrl":"https://doi.org/10.1039/d6py00698a","url":null,"abstract":"Polyurethane foam represents the predominant form of polyurethane materials and is extensively utilized in applications such as thermal insulation, soundproofing, and vibration damping. Owing to its inherently stable covalently cross-linked network, which severely limits reprocessing and remolding, the recycling and reuse of polyurethane foam have long attracted considerable attention in both academic and industrial communities. This review summarizes recent advancements in polyurethane foam recycling enabled by dynamic covalent chemistry. Key topics include the incorporation of dynamic covalent bonds, the associated changes in material properties, and representative recycling methodologies and products, such as densified films, adhesives, re-foamed foams, and 3D-printable resins. Furthermore, current challenges and future prospects are discussed to provide insights into the high-value recycling of polyurethane foams and the sustainable development of the polyurethane industry.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"158 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151993","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}
Hayden R Montgomery, Tong Zhang, Grace E Kunkel, Magdalena F Polite, Jeonghun Lee, Marco S Messina, Alexander M Spokoyny, Heather D Maynard
Organometallic Au(iii) cysteine arylation strategies have recently been employed for efficient and selective conjugation to proteins and peptides. In this work, atom transfer radical polymerization (ATRP) was utilized to synthesize iodophenyl end-functionalized poly(polyethylene glycol methacrylate) (pPEGMA), poly(hydroxyethyl methacrylate) (pHEMA) and poly(2-(dimethylamino)ethyl methacrylate) (pDMAEMA), which were subjected to MeDalPhos-Au(i)Cl to form Au(iii) polymer reagents. The Au(iii)-pPEGMA was reacted with T4-lysozyme (T4L) containing a free thiol to form a T4L-pPEGMA conjugate. In a complementary approach, an Au(iii) ATRP initiator was synthesized for subsequent conjugation to a peptide and T4L to form biomacroinitators. These peptide and protein macroinitiators were then subjected to polymerization conditions to form pDMAEMA conjugates in situ. This work demonstrates that Au(iii) organometallic reagents in conjunction with ATRP offers an efficient strategy for the preparation of protein-polymer conjugates by either grafting to or grafting from approaches.
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