Polymer Chemistry最新文献

Local Cross-Linking Structure Regulates Active Site Mobility and Molecular Accessibility in Polymer-Bound Photocatalysts 局部交联结构调节聚合物结合光催化剂活性位点迁移率和分子可及性

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2026-10-20 DOI: 10.1039/d6py00862c

Hikaru Matsumoto,Masanori Nagao,Yoshiko Miura

{"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}

引用次数: 0

Accessing block copolymers with independently modulated tacticities using sequential cationic–anionic polymerization of vinyl ethers and thiiranes 使用乙烯醚和硫烷的顺序阳离子-阴离子聚合获得具有独立调制策略的嵌段共聚物

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2026-10-19 DOI: 10.1039/d6py00788k

William Ramos,Nicholas M. Legaux,Brandon M. Hosford,Hanlin M. Wang,Elizabeth A. Murphy,Alicia C. Huggett,Frank A. Leibfarth,Jessica R. Lamb

{"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}

引用次数: 0

Thermoresponsive Behaviour of PEG-Based Methacrylate Polymers: Influence of Linear and Star Architectures 聚乙二醇基甲基丙烯酸酯聚合物的热响应行为：线性和星形结构的影响

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2026-10-15 DOI: 10.1039/d6py00821f

Jiahe Wang,Arkadios Marathianos,Minen Cao,Xu Liu,Theoni K Georgiou

{"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}

引用次数: 0

Modulating the Performance of N-Type Organic Conductors through Cyano Substituent Regiochemistry 氰基取代基区域化学对n型有机导体性能的调节

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2026-10-15 DOI: 10.1039/d6py00836d

Zhenjie Ni,Chenzhan Wang,Congze Xu,Anxin Zhao,Linyi Xue,Hongbin Sun,Tongtong Zhao,Hanlin Wang,Wenping Hu

{"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}

引用次数: 0

Stable ketal-crosslinked anion exchange membranes combining ether-free backbones, piperidinium cations, and rigid–flexible networks 稳定的金属交联阴离子交换膜，结合无醚骨架、哌啶离子和刚柔网络

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2026-10-15 DOI: 10.1039/d6py00668j

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

{"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}

引用次数: 0

1,2-Dithiolanes in photodynamic linear and network polymers: current applications and future directions 1,2-二硫代烷在光动力线性和网状聚合物中的应用现状和未来发展方向

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2026-10-15 DOI: 10.1039/d6py00798h

Benjamin R. Nelson,Kristi S Anseth,Christopher N. Bowman

引用次数: 0

Disentangling the Electrochromic and Acidochromic Optical Switching in Multi-Stimuli-Responsive Spiropyran Copolymers 多刺激响应螺吡喃共聚物中电致变色和酸致变色光开关的解缠

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2026-10-14 DOI: 10.1039/d6py00735j

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

{"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}

引用次数: 0

Introduction to dynamic polymer networks 动态聚合物网络导论

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2026-10-12 DOI: 10.1039/d6py90113a

Kristi Anseth,Christopher N. Bowman,Filip E. Du Prez,Tao Xie

引用次数: 0

Polyurethane Foam Recycling Based on Dynamic Covalent Chemistry: Strategies and Perspectives 基于动态共价化学的聚氨酯泡沫回收：策略与展望

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2026-10-12 DOI: 10.1039/d6py00698a

Jing Wang,Yang You

引用次数: 0

Biomolecule-polymer conjugates synthesized by a combination of organometallic bioconjugation and atom transfer radical polymerization. 有机金属生物偶联与原子转移自由基聚合相结合合成的生物分子-聚合物偶联物。

IF 3.9 2区化学

Polymer Chemistry Pub Date : 2026-10-05 DOI: 10.1039/d6py00714g

Hayden R Montgomery, Tong Zhang, Grace E Kunkel, Magdalena F Polite, Jeonghun Lee, Marco S Messina, Alexander M Spokoyny, Heather D Maynard

{"title":"Biomolecule-polymer conjugates synthesized by a combination of organometallic bioconjugation and atom transfer radical polymerization.","authors":"Hayden R Montgomery, Tong Zhang, Grace E Kunkel, Magdalena F Polite, Jeonghun Lee, Marco S Messina, Alexander M Spokoyny, Heather D Maynard","doi":"10.1039/d6py00714g","DOIUrl":"10.1039/d6py00714g","url":null,"abstract":"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.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" ","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13637460/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149101300","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0