Macromolecules最新文献_第5页

Photoresponsive Diarylethene-Based Polyolefins 光响应性二乙烯基聚烯烃

IF 5.7 1区化学

Macromolecules Pub Date : 2026-10-13 Epub Date: 2026-09-21 DOI: 10.1021/acs.macromol.6c02256

Dan Peng, Sijia Cheng, Guifu Si, Menghe Xu, Min Chen

{"title":"Photoresponsive Diarylethene-Based Polyolefins","authors":"Dan Peng, Sijia Cheng, Guifu Si, Menghe Xu, Min Chen","doi":"10.1021/acs.macromol.6c02256","DOIUrl":"10.1021/acs.macromol.6c02256","url":null,"abstract":"Stimuli-responsive polymers are a class of functional materials that can undergo reversible physical or chemical changes in their structure, properties, or functions in response to external stimuli. In this work, we proposed a novel photoresponsive closed-loop polymer design strategy that integrates responsive molecular properties with the closed-loop concept, aiming to effectively address the long-standing challenges associated with the poor responsiveness and inadequate recyclability of traditional polymer materials. By combining the efficiency of ring-opening metathesis polymerization (ROMP) with the intrinsic thermal stability of photoresponsive molecular switches, we reported the (co)polymerization of photoresponsive diarylethene-based (DTE) cyclic monomers. This approach enables the rational design and preparation of photoresponsive polyolefins with tunable structures and properties, including mechanical performance, thermodynamic characteristics, and reversible color variation. We further explored equilibrium-controlled transformations to establish reversible closed-loop pathways for monomer–polymer interconversion. Notably, for the DTE-based homopolymer, a dual closed-loop platform was established via photoinduced transformation and Ru-catalyzed metathesis (de)polymerization. This work provides an efficient platform to advance the sustainable development and practical application of advanced responsive polymers.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"10833–10842"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149010361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Structure–Property Mechanisms in Low-Modulus RAFT-Mediated Triblock Supramolecular Hydrogels: Network Entanglement and Crystalline Domain Control 低模量raft介导的三嵌段超分子水凝胶的结构-性能机制：网络纠缠和晶域控制

IF 5.7 1区化学

Macromolecules Pub Date : 2026-10-13 Epub Date: 2026-09-27 DOI: 10.1021/acs.macromol.6c01249

Jiani Xu, Hanchang Hu, Xia Dong, Qiangqiang Zhao, Jinxin He

{"title":"Structure–Property Mechanisms in Low-Modulus RAFT-Mediated Triblock Supramolecular Hydrogels: Network Entanglement and Crystalline Domain Control","authors":"Jiani Xu, Hanchang Hu, Xia Dong, Qiangqiang Zhao, Jinxin He","doi":"10.1021/acs.macromol.6c01249","DOIUrl":"10.1021/acs.macromol.6c01249","url":null,"abstract":"Hydrogel reinforcement strategies commonly rely on compositional or network-structure regulation, whereas the structure–property relationships of block copolymer hydrogels prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization remain insufficiently understood. Here, we construct bottlebrush-like, inter-crosslinked triblock copolymer hydrogels with tunable block molecular weights using UPy derivatives (UPyMA/UPyHMA) based on quadruple hydrogen-bonding motifs. Two structurally controlled hydrogels, P(AM-b-UPyMA-b-AM) (PUA) and P(AM-b-UPyHMA-b-AM) (PHA), were synthesized. PUA undergoes polymerization-induced self-assembly (PISA), driven by phase separation induced by the Flory–Huggins χ parameter, to form densely packed nanorod structures. Combining tube-model analysis with structural characterization, we establish the relationships among crosslinking-segment molecular weight, apparent entanglement molecular weight (Me), and mechanical properties. Moderate increases in crosslinking-segment molecular weight synergistically enhance network stiffness and entanglement density. The ordered crystalline domains formed by UPy hydrogen bonding, π–π stacking, and hydrophobic interactions enable PUA to reach a fracture strength of 0.13 MPa—comparable to conventional free-radical hydrogels—while its Young’s modulus (0.020 MPa) is only half. The PUA triblock copolymer hydrogel also exhibits a high swelling ratio (2900% in PBS) and slow degradation over 264 h, combining high water absorbency with superior network stability and showing promise for biomedical applications.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"10911–10929"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049757","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Molecular Parameters Favoring Disordered Hyperuniformity in Brush Particle Materials 有利于刷状颗粒材料无序超均匀性的分子参数

IF 5.7 1区化学

Macromolecules Pub Date : 2026-10-13 Epub Date: 2026-09-26 DOI: 10.1021/acs.macromol.6c01734

Jirameth Tarnsangpradit, Maryam Bagheri, Owen Chen, Hanshu Wu, Rongguan Yin, Yunhao Xu, Alamgir Karim, Krzysztof Matyjaszewski, Michael R. Bockstaller

{"title":"Molecular Parameters Favoring Disordered Hyperuniformity in Brush Particle Materials","authors":"Jirameth Tarnsangpradit, Maryam Bagheri, Owen Chen, Hanshu Wu, Rongguan Yin, Yunhao Xu, Alamgir Karim, Krzysztof Matyjaszewski, Michael R. Bockstaller","doi":"10.1021/acs.macromol.6c01734","DOIUrl":"10.1021/acs.macromol.6c01734","url":null,"abstract":"The concurrence of “single crystal-like” uniformity and isotropy of structure and properties is expected to endow disordered hyperuniform (DH) materials with novel property combinations that have fueled interest in DH hybrid materials as a platform for functional material design. For the example of poly(methyl acrylate) (PMA)-tethered silica (SiO2) particles, this work explored the role of brush architecture and linear polymer (PMA) addition on the degree of hyperuniformity of brush particle assembly structures in the bulk and thin-film states. The results reveal that brush “softness” is a critical design parameter for synthesizing brush particle materials that can be reliably processed into disordered hybrid materials. Here, “softness” refers to shallower interaction potentials achieved, for example, by increasing the degree of polymerization or decreasing the grafting density of tethered chains. Interestingly, in the bulk state, the addition of PMA was required to reduce long-wavelength fluctuations below those of a regular liquid reference state. This suggests that blending of ‘soft’ brush particles with isomorphous linear polymers could present a path for the deliberate fabrication of DH hybrid materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"10748–10759"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049758","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Liquid–Solid Interfacial Fusion Assembly Enables Programmable Chain Density for Controlling Polymer–Mineral Interactions 液-固界面融合组装使可编程链密度控制聚合物-矿物相互作用

IF 5.7 1区化学

Macromolecules Pub Date : 2026-10-13 Epub Date: 2026-09-25 DOI: 10.1021/acs.macromol.6c02018

Dan Yang, Qin Li, Xiaohong Hu, Boxiang Peng, Pei Liu, Biao Xiong, Xia Sun, Yin Ning

{"title":"Liquid–Solid Interfacial Fusion Assembly Enables Programmable Chain Density for Controlling Polymer–Mineral Interactions","authors":"Dan Yang, Qin Li, Xiaohong Hu, Boxiang Peng, Pei Liu, Biao Xiong, Xia Sun, Yin Ning","doi":"10.1021/acs.macromol.6c02018","DOIUrl":"10.1021/acs.macromol.6c02018","url":null,"abstract":"Biomineralization offers key insights into nature’s design of hierarchical materials with exceptional properties. However, progress is hindered by limited molecular-level understanding of organic–inorganic interfacial interactions, particularly how organic matrix structure directs mineral formation and organization. Herein, we synthesize a series of poly(methacrylic acid)x-block-poly(benzyl methacrylate)y (Mx-By) nanoparticles with varying block lengths via polymerization-induced self-assembly, followed by their fusion onto mesoporous silica surfaces through liquid–solid interfacial fusion assembly. This approach yields silica-copolymer core–shell composite nanoparticles with tunable interfacial structures. We show that the packing density of copolymer chains on the fused layer is governed by the degree of polymerization of the hydrophobic block (By). This tunability provides a model platform to systematically investigate how surface chain density dictates polymer–mineral interactions. It is demonstrated that the surface chain density plays a decisive role in controlling the spatial distribution of guest species within mineral phases. We reveal the underlying mechanism behind this interesting phenomenon, which is widespread in natural biominerals. This work not only offers new insights into biomineralization but also provides new design rules for engineering composite crystals with tunable internal compositions and structures.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"10770–10780"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149049800","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Crystallinity-Controlled Reaction Zones and Adhesion at Thermoset/Semicrystalline Polymer Interfaces 热固性/半结晶性聚合物界面的结晶控制反应区和粘附

IF 5.5 1区化学

Macromolecules Pub Date : 2026-10-13 DOI: 10.1021/acs.macromol.6c01015

Shunta Tamura,Tatsuki Abe,Keiji Tanaka

{"title":"Crystallinity-Controlled Reaction Zones and Adhesion at Thermoset/Semicrystalline Polymer Interfaces","authors":"Shunta Tamura,Tatsuki Abe,Keiji Tanaka","doi":"10.1021/acs.macromol.6c01015","DOIUrl":"https://doi.org/10.1021/acs.macromol.6c01015","url":null,"abstract":"Adhesion between thermosetting and semicrystalline thermoplastic polymers depends not only on interfacial chemistry but also on the spatial distribution of reaction products across the interface, yet how polymer crystallinity controls this distribution remains unclear. Here, we investigate how the crystallinity of polyamide 6 (PA6) controls the development of interfacial reaction zones and adhesion strength at epoxy resin (ER)/PA6 interfaces. PA6 films with different crystallinities were prepared, and their buried interfaces with ER were analyzed using atomic force microscopy, infrared spectroscopy, and gas cluster ion beam-assisted X-ray photoelectron spectroscopy. While comparable relative amounts of covalent bonds were detected at the nominal interface, PA6 with low crystallinity exhibited a markedly broader reaction zone due to enhanced penetration of reactive epoxy species into amorphous regions. In contrast, PA6 with high crystallinity confined covalent ester or urethane formation to a narrow interfacial region. Wedge tests revealed substantially higher fracture energy for laminates containing PA6 with low crystallinity, demonstrating that the spatial extent and continuity of the interfacial reaction zone, rather than its interfacial density alone, determine adhesion performance. These findings provide a molecular-level insight into crystallinity-controlled adhesion at thermoset/semicrystalline thermoplastic interfaces.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"10 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Laplace Pressure-Enabled Radical Ring-Opening Polymerization of a Thionolactone 硫代内酯的拉普拉斯压力自由基开环聚合

IF 5.7 1区化学

Macromolecules Pub Date : 2026-10-13 Epub Date: 2026-06-23 DOI: 10.1021/acs.macromol.6c01012

Kaito Fuji, Yukiya Kitayama, Atsushi Harada

{"title":"Laplace Pressure-Enabled Radical Ring-Opening Polymerization of a Thionolactone","authors":"Kaito Fuji, Yukiya Kitayama, Atsushi Harada","doi":"10.1021/acs.macromol.6c01012","DOIUrl":"10.1021/acs.macromol.6c01012","url":null,"abstract":"The reactivity of radical polymerization systems is traditionallydictated by molecular design, while physical parameters such as pressureare seldom considered tools for reaction control. Here, we demonstratethat nanoscale pressure can be deliberately harnessed as a reactiondesign parameter to unlock otherwise inaccessible radical ring-openingpathways. Using miniemulsion polymerization as a nanoconfined reactionplatform, Laplace pressure generated within nanoscale droplets enablesthe ring-opening copolymerization of a thionolactone monomer previouslydeemed inactive, yielding degradable vinyl copolymers. This pressure-assistedreactivity is further amplified by radical compartmentalization, whichsuppresses bimolecular termination. Independent experiments conductedin a high-pressure bulk solution confirm that pressure alone governsthe observed activation, disentangling it from interfacial or confinementeffects. More broadly, this work establishes pressure-enabled chemistryas a versatile strategy for expanding the accessible reaction spaceof radical polymerization, providing a general pathway to degradablevinyl materials without increasing molecular complexity.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"10855–10863"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148336279","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Objective, Accurate, and Efficient Modeling of Macromolecular Assembly Behaviors via an AI-Powered Automated Dissipative Particle Dynamics Framework 通过人工智能驱动的自动耗散粒子动力学框架客观，准确和有效的大分子组装行为建模

IF 5.7 1区化学

Macromolecules Pub Date : 2026-10-13 Epub Date: 2026-07-23 DOI: 10.1021/acs.macromol.6c00826

Minghao Wang, Yi Zheng, Yiwei Wang, Rongrong Zou, Yalei Zeng, Yeqiang Zhou, Yang Liu, Mingming Ding

{"title":"Objective, Accurate, and Efficient Modeling of Macromolecular Assembly Behaviors via an AI-Powered Automated Dissipative Particle Dynamics Framework","authors":"Minghao Wang, Yi Zheng, Yiwei Wang, Rongrong Zou, Yalei Zeng, Yeqiang Zhou, Yang Liu, Mingming Ding","doi":"10.1021/acs.macromol.6c00826","DOIUrl":"10.1021/acs.macromol.6c00826","url":null,"abstract":"The diverse phase behaviors of macromolecules fundamentallygoverntheir mesoscopic morphologies and macroscopic functional properties,broadening their utility across diverse applications. While dissipativeparticle dynamics (DPD) is crucial for characterizing mesoscale phasebehaviors and thermodynamic properties, its predictive power in complexsystems is severely restricted. This limitation stems from the subjectivenature of traditional coarse-grained (CG) mapping and the computationalexigencies required for accurate parametrization. Herein, we introduceone-button DPD (OB-DPD), an automated framework that integrates graph-theoreticCG mapping with artificial intelligence-driven prediction to facilitateseamless, high-fidelity parametrization. It drastically compressesthe traditional multiday preprocessing cycle into seconds. We demonstrateOB-DPD’s robustness across diverse systems, ranging from smallmolecules to complex polymers. Furthermore, we successfully predictedand experimentally validated the assembly behaviors of a novel triblockcopolymer. By streamlining the workflow from molecular design to characterization,this data-driven framework accelerates the development of macromolecularmaterials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"10723–10735"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148564619","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Nonlinear Elasticity of Entangled Networks and Gels 纠缠网络和凝胶的非线性弹性

IF 5.7 1区化学

Macromolecules Pub Date : 2026-10-13 Epub Date: 2026-09-14 DOI: 10.1021/acs.macromol.6c02088

Andrey V. Dobrynin

{"title":"Nonlinear Elasticity of Entangled Networks and Gels","authors":"Andrey V. Dobrynin","doi":"10.1021/acs.macromol.6c02088","DOIUrl":"10.1021/acs.macromol.6c02088","url":null,"abstract":"We develop a molecular theory of the nonlinear elasticity of entangled polymer networks and gels that incorporates both strand rigidity and finite extensibility. Network strands are represented by Toeplitz chains of correlated Gaussian bonds, with the bond-correlation parameter determining the Kuhn length. A self-consistent constraint on the mean-square bond length produces finite chain extensibility and a force–extension relation that connects the Hookean, worm-like chain, and freely jointed chain deformation regimes. For affine networks, the model predicts a crossover from a rigidity-dependent, worm-like strand response at intermediate deformation to a universal freely jointed strand divergence near full extension. Entanglements are introduced through an anisotropic tube-like potential connecting a strand to a nonfluctuating network background. Its construction ensures that affine deformation of the average tube path does not itself generate elastic energy; the entanglement contribution instead originates from suppression of strand fluctuations within the deformed tube. Normal mode analysis yields self-consistent expressions for the free energy and stress of entangled networks with finitely extensible strands. The model predicts a nonmonotonic Mooney stress and broken compression–extension symmetry, with both branches approaching the same finite-extensibility divergence. In swollen gels, swelling narrows the accessible deformation interval, softens the intermediate response, and rapidly suppresses the entanglement modulus. The cross-link modulus decreases more slowly than predicted by Gaussian network theory and diverges near full strand extension, whereas the entanglement modulus varies nonmonotonically and passes through a negative minimum.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"11001–11015"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148974100","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Poly(aryl piperidinium-co-tetramethylpiperidinyl oxide) Copolymers with Intrinsic Antioxidant Capability for Anion Exchange Membrane Water Electrolysis 阴离子交换膜电解用具有固有抗氧化性能的聚芳基胡椒酰-共四甲基环氧胡椒酰共聚物

IF 5.7 1区化学

Macromolecules Pub Date : 2026-10-13 Epub Date: 2026-09-14 DOI: 10.1021/acs.macromol.6c01221

Hanyu Zhu, Xinao Yu, Shangbin Jin

{"title":"Poly(aryl piperidinium-co-tetramethylpiperidinyl oxide) Copolymers with Intrinsic Antioxidant Capability for Anion Exchange Membrane Water Electrolysis","authors":"Hanyu Zhu, Xinao Yu, Shangbin Jin","doi":"10.1021/acs.macromol.6c01221","DOIUrl":"10.1021/acs.macromol.6c01221","url":null,"abstract":"Anion exchange membranes (AEMs) for water electrolysis may suffer from oxidative degradation under high-potential operating conditions due to the attack of reactive oxygen species (ROS). Addressing the oxidative durability challenge for high-performancewater electrolysis remains imperative. Here, we report the preparation of AEMs with intrinsic antioxidant capability by directly copolymerization of nitroxide radicals into poly(aryl piperidinium) copolymer backbones. A series of TEMPO-containing AEMs (TEMPO-PAP-x%) are synthesized by incorporation of 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl (4-oxo-TEMPO). The resulting TEMPO-PAPs based membranes exhibit high hydroxide conductivity and tensile strength. Remarkably, after 480 h of immersion in Fenton’s reagent (3 ppm FeSO4, 1% H2O2), the TEMPO-PAP membrane could retain 99.25% of its mass, whereas pristine PAP retains only 81.77%. Electron paramagnetic resonance (EPR) spectroscopy confirms that the nitroxide radicals are consumed during radical attack, acting as efficient radical scavengers. In water electrolysis tests, the TEMPO-PAP-10% membrane delivers an outstanding current density of 5.65 A cm–2 at 2.0 V (80 °C, 1 M KOH), representing a 175% enhancement over PAP. This work establishes a new strategy for endowing AEMs with intrinsic antioxidant stability.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"11197–11204"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148974101","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Branching Architecture Enhances Polyion Complex Formation beyond Overall Charge under Weakly Cationic Conditions 在弱阳离子条件下，分支结构增强了多离子络合物的形成

IF 5.7 1区化学

Macromolecules Pub Date : 2026-10-13 Epub Date: 2026-09-17 DOI: 10.1021/acs.macromol.6c01748

Sachi Ibuki, Masayuki Nakashoya, Hiina Danno, Jin Motoyanagi, Nobuhiro Nishiyama, Tomohiro Umeno, Makoto Oba, Hiroyasu Takemoto

{"title":"Branching Architecture Enhances Polyion Complex Formation beyond Overall Charge under Weakly Cationic Conditions","authors":"Sachi Ibuki, Masayuki Nakashoya, Hiina Danno, Jin Motoyanagi, Nobuhiro Nishiyama, Tomohiro Umeno, Makoto Oba, Hiroyasu Takemoto","doi":"10.1021/acs.macromol.6c01748","DOIUrl":"10.1021/acs.macromol.6c01748","url":null,"abstract":"Branched polyelectrolytes form more stable polyion complexes (PICs) than their linear counterparts, yet whether this reflects an intrinsic effect of architecture or merely the higher overall charge that usually accompanies branching has remained unresolved. Here, we address this question using a series of pH-responsive polyzwitterions, poly(glutamate) derivatives bearing ethylenediamine-based carboxybetaine side chains (PGlu(DET-Car)). Within this platform, the number of arms was designed to be varied while maintaining identical side-chain chemistry and comparable overall charge. The stepwise protonation of the ethylenediamine moieties generates a weakly cationic state over the pH range of 6–7. In this weakly charged regime, the dominant contribution of net charge is minimized, allowing the subtle effects of molecular architecture on electrostatic interactions to be resolved. We find that increasing the number of arms markedly enhances interactions with flexible polyanions, whereas no such enhancement occurs for a rigid low-molecular-weight anionic probe. These results establish that regions of locally elevated charge density, which tend to form within branched architectures, promote cooperative, multivalent interactions that are inaccessible to linear chains of equivalent overall charge. The molecular architecture thus represents an independent design parameter for PIC formation, complementary to overall charge and chain length.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"59 19","pages":"10676–10686"},"PeriodicalIF":5.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148985081","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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