{"title":"Modular Synthesis of Amphiphilic Ionic Polyacrylamides for Noncovalent Modulation of Esterase Activity","authors":"Seth E. Chislea, Junfeng Chen","doi":"10.1002/macp.70331","DOIUrl":"https://doi.org/10.1002/macp.70331","url":null,"abstract":"<div>\u0000 \u0000 <p>Engineering the local environment of enzymes provides a complementary strategy to protein engineering for improving biocatalyst performance under process-relevant conditions. Here, a modular post-polymerization modification platform based on poly(pentafluorophenyl acrylate) (poly(PFPA)) is used to prepare a focused library of amphiphilic ionic polyacrylamide-based copolymers with systematic variation in degree of polymerization, ionic/hydrophilic composition, and hydrophobic side-chain length. Limiting first-stage aminolysis installs trimethylammonium, oligo(ethylene glycol), and alkyl side chains, whereas residual activated esters are subsequently capped as propylamides or hydrolyzed to carboxylates. In a parallel microplate fluorogenic esterase assay, the polymers produce distinct concentration-dependent changes in apparent enzyme activity. High polymer concentrations generally inhibit product formation, whereas selected C6- and C10-containing polymers, especially at DP 60 and 100, increase apparent esterase activity at low concentrations by approximately 20% relative to the enzyme-only control. C16 analog are predominantly inhibitory, consistent with overly strong hydrophobic association, self-assembly, or substrate sequestration, whereas PEG incorporation attenuates both activation and inhibition, and zwitterionic charge balance partially mitigates hydrophobe-induced inhibition. These results identify hydrophobicity, multivalency, and charge balance as coupled design variables in noncovalent polymer-enzyme complexation and establish a practical framework for screening synthetic polymer microenvironments for hydrolase catalysis.</p>\u0000 </div>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"227 16","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148848689","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Click-Engineered 1,2,3-Triazole-Tethered Polyurethanes: Molecular Design, Structure-Property Relationships, and Potential Antifouling Behavior","authors":"Kashmiri Borah, Shaikh Sumaiya Akhtar, Kavya Lekha Sunkara, Aruna Palanisamy, Sunil Misra","doi":"10.1002/macp.70327","DOIUrl":"https://doi.org/10.1002/macp.70327","url":null,"abstract":"<div>\u0000 \u0000 <p>A compelling strategy to integrate contact-active, non-leaching functionalities directly within the polyurethane (PU) backbone is the covalent incorporation of heterocyclic structures. To investigate the influence of triazole-based molecular architecture on polyurethane properties, triazole-based dihydrazide chain extenders bearing C8 and C12 pendant alkyl chains were synthesized via Cu(I)-catalyzed azide-alkyne cycloaddition and incorporated into thermoplastic polyurethanes (TPUs). Thermal analysis revealed composition-dependent stability governed by the interplay of triazole incorporation, side-chain length, hard-segment content, and diisocyanate structure. Systematic variation of pendant alkyl chain length, polyol molar mass, diisocyanate structure, and NCO/OH ratio demonstrated that molecular architecture governs molar mass distribution, microphase separation, storage modulus, and glass transition behavior. Increasing hard-segment content and hydrophobic triazole substituents progressively increased surface hydrophobicity, with water contact angles reaching approximately 115°. Antimicrobial evaluation against <i>Escherichia coli</i> (Gram-negative), <i>Staphylococcus aureus</i> (Gram-positive), and <i>Candida albicans</i> (fungal strain) demonstrated reduced microbial adhesion on triazole-functionalized TPU surfaces despite the absence of diffusional antimicrobial activity, indicating non-leaching, contact-active antifouling behavior. Furthermore, an optimized formulation yielded a preliminary waterborne dispersion that formed mechanically robust free-standing films, demonstrating the feasibility of future environmentally friendly waterborne polyurethane coating systems.</p>\u0000 </div>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"227 16","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148784747","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Suzanne Grace Aubin, Annette Monika Schmidt, Marc Christian Leimenstoll
{"title":"Novel RAFT Agent Synthesis for the Preparation of Polystyrene Diol Oligomers for Polyurethane Synthesis","authors":"Suzanne Grace Aubin, Annette Monika Schmidt, Marc Christian Leimenstoll","doi":"10.1002/macp.70326","DOIUrl":"https://doi.org/10.1002/macp.70326","url":null,"abstract":"<div>\u0000 \u0000 <p>The features of versatile and widely used polyurethanes (PU) are largely determined by the intrinsic properties of the used oligomer polyols. Commonly used polyols are polyether (PEP), polyester (PES), and polycarbonate (PC) diols. In addition to these, vinyl-based compounds like oligomeric styrenes or acrylics provide benefits in terms of property improvement. The synthesis of such polyols yielding so-called hybrid systems relies on chain growth reactions that represent severe challenges regarding the implementation of well-defined OH-(end)functionality. Controlled radical polymerization techniques like reversible-addition-fragmentation chain-transfer polymerization (RAFT) are known to be capable of implementing well-defined termini. Here, we report on an effective synthesis route to a RAFT agent for the production of well-defined OH-terminated styrene oligomer diols, in order to expand the toolbox of building blocks for PU synthesis.</p>\u0000 </div>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"227 16","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148784231","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Photoinduced Flow Cationic RAFT Polymerization Using Diphenyliodonium Salt as Photoacid Generator","authors":"Xiaoyuan Liu, Jiajia Li, Qi Shi, Xia Lin, Na Li, Jian Zhu","doi":"10.1002/macp.70329","DOIUrl":"https://doi.org/10.1002/macp.70329","url":null,"abstract":"<div>\u0000 \u0000 <p>Living cationic polymerization (LCP) under mild and scalable conditions remains a longstanding challenge due to the intrinsic sensitivity of cationic species. Herein, we report a metal-free, visible-light-induced cationic reversible addition–fragmentation chain transfer (RAFT) polymerization of vinyl ethers in a continuous-flow microreactor using diphenyliodonium hexafluorophosphate (DPI) as a commercially available photoacid generator (PAG). The integration of photochemistry with flow processing enables precise control over polymerization at room temperature without rigorous reagent purification or an inert atmosphere. The system affords polymers with predictable molecular weights, narrow molecular weight distributions, and excellent end-group fidelity, as evidenced by kinetic analysis and successful block copolymerization. The enhanced mass, heat, and photon transfer in the microreactor effectively mitigates local heat accumulation and ensure uniform irradiation, overcoming key limitations of batch processes. Furthermore, a broad range of vinyl ether monomers can be polymerized in a controlled manner, and copolymerization allows tunable thermal properties. This work establishes a robust and scalable platform for controlled cationic polymerization, offering new opportunities for the development of metal-free photopolymerization technologies in continuous flow.</p>\u0000 </div>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"227 16","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148784220","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Biobased Thermosets with an All-Hydrocarbon Backbone: A Platform Enabling Fully Multicomponent Closed-Loop Chemical Recyclability","authors":"Wei Sun, Xin Min, Yuan Hu, Puyou Jia, Ye Sha","doi":"10.1002/macp.70328","DOIUrl":"https://doi.org/10.1002/macp.70328","url":null,"abstract":"<div>\u0000 \u0000 <p>Conventional petroleum-based thermosetting resins, characterized by their three-dimensional crosslinked networks, offer outstanding performance yet are plagued by challenges related to incomplete degradation and low recycling efficiency. Current recovery methods relying on degradable heteroatom bonds are further constrained by poor environmental resistance and the difficulty of recovering crosslinking components. To address these limitations, this study proposes a novel design strategy for biomass-derived thermosetting resins based on low ring-strain building blocks. Using alcohol derivatives from biomass (including coconut oil, straw, and corn starch) as raw materials, we synthesized a monofunctional cyclooctene monomer and multifunctional crosslinkers, subsequently constructing oil-based thermosetting resins with all-carbon backbones via ring-opening metathesis polymerization (ROMP). The resulting biobased resins exhibit excellent thermal stability (<i>T</i><sub>d,5%</sub> > 340°C) and precisely tunable glass transition temperatures. The low ring-strain imparted by the ketal-modified building units enables controlled depolymerization of the resin via olefin metathesis under mild conditions (50°C). This process achieves the simultaneous recovery of both the pristine monomer and crosslinkers, with a maximum total recovery rate of 95.6%, thus establishing a fully reactant closed-loop chemical recycling system. This work provides a new strategy for their green synthesis and offering robust support for the low-carbon, sustainable development of polymeric materials.</p>\u0000 </div>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"227 16","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148784219","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lu Bai, Sina Ghiassinejad, Yinghui Zhang, Xuesong Wu, Feili Lai, He Jia, Jean-François Gohy
{"title":"Solid Polymer Electrolytes Based on Statistical Polyurethanes","authors":"Lu Bai, Sina Ghiassinejad, Yinghui Zhang, Xuesong Wu, Feili Lai, He Jia, Jean-François Gohy","doi":"10.1002/macp.70324","DOIUrl":"https://doi.org/10.1002/macp.70324","url":null,"abstract":"<div>\u0000 \u0000 <p>Poly(ethylene oxide) (PEO) is one of the most widely used materials for solid polymer electrolytes (SPEs). However, the high crystallinity and low ionic transference numbers of conventional PEOs are hindering their utilization in lithium metal batteries, except at temperatures above the melting point of PEO at ca. 60°C. Different strategies have thus been examined over the years to decrease the crystallinity of PEO. Here, we use α,ω-dihydroxy PEO of low molar mass and a diol containing an aromatic pyridine group as comonomers in a step-growth polymerization with a diisocyanate to obtain statistical polyurethanes. SPEs are obtained by mixing the polyurethanes with different amounts of LiTFSI. We thoroughly characterize the different investigated combinations by differential scanning calorimetry to determine crystallinity, rheology to assess mechanical properties, and temperature-dependent ionic conductivity, linear sweep voltammetry, and lithium-ions transference number measurements to discriminate the best candidates for SPEs. We demonstrate that the statistical distribution of the comonomers in the PUs effectively decreases the crystallization degree of PEO segments, while the presence of urethanes and aromatic amine functional groups allows better transport of lithium ions.</p>\u0000 </div>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"227 15","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148753044","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Polymorphic Crystalline Structure and Properties of Polyamides","authors":"Zhihao Lin, Weihong Zeng, Yunqi Xu, Kejian Yang, Wanding Chen, Xuyi Fan, Zhongke Yuan, Cheng Wang, Xudong Chen","doi":"10.1002/macp.70323","DOIUrl":"https://doi.org/10.1002/macp.70323","url":null,"abstract":"<div>\u0000 \u0000 <p>The polymorphic supermolecular structure of semicrystalline polymers exerts a decisive influence on their macroscopic properties, which is particularly pronounced in polyamide systems dominated by hydrogen bonding. This paper collates the formation mechanisms, regulation strategies and structure-property relationships between polymorphic structures and macroscopic properties of polyamide systems reported in recent years. The regulation methods for the polymorphic crystalline structure of polyamides, based on polymorphism and Brill transition behavior, are categorized into three types: chemical methods involving random copolymerization and block copolymerization; physical methods including polymer blending, nucleating agent incorporation and solution induction; and processing methods such as stretching, shear fields, temperature fields and their coupled fields. The comprehensive properties of polyamides, especially mechanical, thermal, barrier and optical properties, can be effectively tailored via the regulation of their crystalline structures. By systematically reviewing the existing research progress, this review aims to deepen the understanding of the evolution mechanism of polyamide polymorphism and provide novel insights for the development of high-performance polyamide materials.</p>\u0000 </div>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"227 15","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148696282","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Functionalization of Dual-Stimuli Responsive Double-Network Hydrogels With Silver Nanoparticles for Antibacterial Performance","authors":"Himanshi Chaurasia, Akansha Dixit, Neha Yadav, Sourabh Singh, Santosh Kumar Misra, Ramkrishna Sarkar","doi":"10.1002/macp.70315","DOIUrl":"https://doi.org/10.1002/macp.70315","url":null,"abstract":"<div>\u0000 \u0000 <p>In this report, hydrogels were combined with silver nanoparticles to impart antibacterial properties, yielding robust materials that prevent bacterial infections while maintaining stimulus responsiveness. The antibacterial hydrogel was based on double-network (DN) hydrogels and prepared via in situ reduction of silver nitrate to silver nanoparticles (AgNPs). The DN hydrogel consists of polyvinyl alcohol-<i>co</i>-glutaraldehyde and poly(acrylamide-<i>co</i>-sodium acrylate-<i>co</i>-N-isopropylacrylamide), serving as the first and second networks, respectively. The FT-IR, x-ray diffraction, and TEM analysis revealed the successful incorporation of silver nanoparticles within the DN hydrogel. The stimulus responsiveness of these hydrogels was assessed through temperature- and pH-dependent swelling, and their thermal properties were also evaluated. The antibacterial efficacy of AgNPs embedded in DN hydrogels was validated by optical density (OD<sub>600</sub>) measurements in suspension culture, which confirmed significant growth inhibition of both <i>Escherichia coli</i> (Gram-negative) and <i>Staphylococcus aureus</i> (Gram-positive) bacteria. Interestingly, the assessment of antibacterial activity using an agar diffusion assay with silver nanoparticle-loaded hydrogels also revealed excellent bacterial growth inhibition against both <i>Escherichia coli</i> and <i>Staphylococcus aureus</i> (p < 0.0001). Hydrogels also showed notable cytocompatibility. These findings highlight the potential of AgNPs-embedded stimuli-responsive DN nanocomposite hydrogels, which may serve as promising materials for various biomedical products that require an antibacterial microenvironment.</p>\u0000 </div>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"227 15","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148696116","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Dynamic Vulcanization and Structure-Property Relationship of High-Performance Fluoroelastomer/Polyamide-12 Thermoplastic Elastomeric Blends","authors":"Kartikeya Dubey, Chirag Sonagara, Jotin Singh Malhan, Subhan Salaeh, Bhabani K. Satapathy, Shib Shankar Banerjee","doi":"10.1002/macp.70310","DOIUrl":"https://doi.org/10.1002/macp.70310","url":null,"abstract":"<div>\u0000 \u0000 <p>High-performance thermoplastic vulcanizates (TPVs) from fluorinated elastomers are constrained by intrinsic immiscibility, inadequate interfacial adhesion, and restricted melt-processability. In this study, these challenges are addressed by designing novel fluoroelastomer (FKM)/polyamide-12 (PA12) (60/40 w/w) TPVs via dynamic vulcanization using a diamine curing agent. This study thoroughly investigates the relationship between dynamic vulcanization, microstructural development, and the resulting mechanical, dynamic mechanical, and oil swelling resistance properties. Torque-time curves show that elastic resistance grows as the curative loading increases from 0.5 to 2 php, suggesting the gradual formation of rubbery networks within the FKM domains and enhanced melt cohesion of the TPVs. Frequency-sweep test revealed shear-thinning behavior at low frequency, aligning with an elastically linked rubber phase dispersed in a continuous PA12 matrix. Controlled dynamic vulcanization substantially improved phase morphology, reducing FKM domain size from ∼3.6 µm in the uncured (neat blend) to ∼2.0 µm at 2.0 php. Interestingly, upon dynamic vulcanization, the glass transition temperature (<i>T<sub>g</sub>)</i> values of FKM and PA12 shifted toward each other, indicating improved interdomain interactions between the phases. The microstructural changes and interdomain interactions significantly improved the mechanical properties, showing a twofold increase in tensile strength and a sixfold rise in elongation at break compared to the uncured specimen (neat blend) at the highest curative level (2 php). The developed TPVs showed outstanding oil swelling resistance, with only 0.5–2.5% volume swell in ASTM oil #3 at 150°C over 72 h, among the lowest reported for this type of TPVs and enhanced thermal stability, both increasing with vulcanization level.</p>\u0000 </div>","PeriodicalId":18054,"journal":{"name":"Macromolecular Chemistry and Physics","volume":"227 15","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148695939","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}