Macromolecules最新文献

{"title":"Aromatic Residues Drive Polyelectrolyte Coacervates into Hydrogels for Underwater and Underoil Adhesion","authors":"Zhili Zhang, Yonglin He, Ting Wang, Xiaoyuan Wang, Hongguang Liao, Misaki Sawada, Xiang Li, Hailong Fan, Jian Ping Gong","doi":"10.1021/acs.macromol.5c02575","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02575","url":null,"abstract":"Liquid–liquid phase separation (LLPS) of intrinsically disordered proteins (IDPs), followed by a liquid–solid transition, plays a crucial role in wet adhesion in natural systems. Although the mechanisms underlying these phase transitions are not fully understood, the presence of evenly distributed cationic and aromatic groups in IDPs is believed to facilitate the process. Inspired by this molecular feature, we designed a hydrophobic polyelectrolyte (Pcπ) with statistically distributed cationic and aromatic residues. Pcπ undergoes LLPS through complexation with phytic acid (PA), followed by a spontaneous transition into gel-like films in aqueous media. These Pcπ–PA films exhibit robust adhesion both underwater and under oil, outperforming conventional coacervate-based adhesives. In contrast, a corresponding polyelectrolyte in which the aromatic residues were substituted with methyl groups forms only liquid-like coacervates. This study highlights the critical role of aromatic residues in LLPS and phase transitions, offering valuable insights into developing protein-inspired adhesives capable of functioning in complex environments.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"11 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209705","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}

{"title":"Effects of Knotting on the Collapse of Active Ring Polymers","authors":"Davide Breoni, Emanuele Locatelli, Luca Tubiana","doi":"10.1021/acs.macromol.5c02097","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02097","url":null,"abstract":"We use numerical simulations to study tangentially active flexible ring polymers with different knot topologies. Simple, unknotted active rings display a transition from an extended phase to a collapsed one upon increasing the degree of polymerization. We find that topology has a significant effect on the polymer size at which the collapse takes place, with twist knots collapsing earlier than torus knots. Increasing knot complexity further accentuates this difference, as the collapse point of torus knots grows linearly with the minimum crossing number of the knot while that of twist knots shrinks, eventually canceling the actively stretched regime altogether. This behavior is a consequence of the ordered configuration of torus knots in their stretched active state, featuring an effective alignment for non-neighboring bonds which increases with the minimal crossing number. Twist knots do not feature ordered configurations or bond alignment, increasing the likelihood of collisions, leading to collapse. These results show that topology yields a degree of control on the properties of active ring polymers, and can be used to tune them. At the same time, they suggest that activity might introduce a bias for torus knots, as complex twist knots cannot be formed in extended active polymers.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"42 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209704","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}

{"title":"Tailoring the Morphology Transformation and Simultaneous Generation of Bimodal Patterns through Directed Self-Assembly of Binary Cylindrical Block Copolymer/Homopolymer Blends","authors":"Zhiyong Wu, Huangyan Shen, Junying Yang, Jiacheng Luo, Jiaxiang Li, Xingran Xu, Jianghao Zhan, Zili Li, Qingshu Dong, Weihua Li, Shisheng Xiong","doi":"10.1021/acs.macromol.5c01087","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01087","url":null,"abstract":"Lithography with directed self-assembly (DSA) has demonstrated significant potential in fabricating integrated circuits, particularly in logic and memory chips with periodic patterns. However, it is challenging to achieve asymmetrical line patterns with block copolymers (BCPs) that meet the manufacturing requirements of integrated circuits. We propose a binary cylindrical BCP/homopolymer blending strategy to generate asymmetric multiple line patterns. By carefully tailoring the blending rates of homopolymer poly(methyl methacrylate) (hPMMA) with different molecular weights in cylindrical polystyrene-<i>b</i>-poly(methyl methacrylate), we manipulate the morphology transformation, period, and PMMA duty cycle (space width relative to the pitch) of BCP/hPMMA self-assembly. Specifically, we employ a BCP/hPMMA blend to fine-tune the process window of asymmetric multiple line patterns with the aid of PS-affined topographical templates. This approach highlights the superiority of line pattern quality in the blends compared to the symmetric lamellar BCP. Moreover, the simultaneous generation of bimodal line and hole patterns was achieved through a one-step DSA process with one BCP/hPMMA blend. Furthermore, self-consistent field theory simulation was employed to explore the self-assembly of BCP/homopolymer blend in confined guiding templates, and the results were in good consistency with the experimental results. This strategy provides an essential technological platform for the fabrication of asymmetrical line and hole patterns with various resolutions and complex metal layers.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"10 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209936","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}

{"title":"Frustrated Lewis Pair-Mediated Catalyst Efficiency in ROMP: Mechanistic Insights from Boronic Ester-Functionalized Monomers","authors":"Sitong Feng, Xin Zhang, Yuanzhi Li, Feng Yu, Zhen Dong, Zhiqiang Sun, Zhong-Ren Chen","doi":"10.1021/acs.macromol.5c01553","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01553","url":null,"abstract":"The ring-opening metathesis polymerization (ROMP) of boronic ester-functionalized monomers remains underexplored compared with other polymerization strategies, despite the unique physical and chemical properties offered by boronic esters. Herein, we report an unrecognized mechanistic insight into which boronic ester-functionalized monomers modulate ROMP kinetics via frustrated Lewis pair (FLP) interactions. In situ nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) calculations reveal that the boron atoms in norbornylboronic acid pinacol ester (NB-Bpin) and norbornylboronic acid dibutyl ester (NB-B(OBu)₂ ) can associate with tricyclohexylphosphine (PCy₃) ligands of Grubbs’ catalyst, forming FLPs that shift the ligand-catalyst binding equilibrium toward active ruthenium species. This FLP-mediated mechanism increases the polymerization rate proportionally to monomer concentration, with NB-B(OBu)₂ (flexible butoxy groups) exhibiting a 3.75-fold enhancement compared with a 1.26-fold increase for NB-Bpin (rigid five-membered pinacol boronate). In contrast, methylnorbornylboronic acid pinacol ester (MNB-Bpin), designed with a methyl group adjacent to the boron atom to suppress FLP formation, shows no enhancement in the polymerization rate. Crucially, the weak interaction nature of FLP allows PCy₃ to dissociate completely from the polymer product, preserving the material’s intrinsic properties. The resulting boronic ester-functionalized polymer exhibits high thermal stability, optical transparency (&gt;91% ), and dynamic covalent cross-linking characteristics. By elucidating the monomer-ligand interactions in ROMP, this study demonstrates the potential of these FLPs in modulating the catalyst efficiency, and offers broad implications for diverse reaction systems.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"118 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183036","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}

{"title":"Identifying Memory Effects in Short-Time Dynamics of Polymer Systems by Machine Learning","authors":"Kaihua Zhang, Yongzhi Ren, Shuanhu Qi, Ying Jiang","doi":"10.1021/acs.macromol.5c01522","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01522","url":null,"abstract":"Memory effects are intrinsic properties of flexible macromolecular systems emerging originally from their hierarchical microstructures and multiscale dynamic behaviors of polymer chains during nonequilibrium processes. The nonlocal temporal dependence of transport coefficients (e.g., the Onsager coefficient), a fundamental manifestation of memory effects that govern the dynamic evolution of collective observables, still poses significant challenges for analytical formulations. Herein, we propose a machine-learning-based framework to extract the history-dependent Onsager coefficient directly from the density evolution data, generated from particle-based single-chain in mean-field simulations, thereby enabling these coefficients to accurately capture underlying microscopic characteristics. This framework, termed the dynamic density functional theory-ordinary differential equation (DDFT-ODE) Net, embeds equations of DDFT into the ODE network, enhancing the physical consistency and computational efficiency of the framework. Our study of the relaxation of density fluctuations in an ideal symmetric diblock copolymer melt reveals that memory effects play a dominant role in determining density evolution processes at early times. Further analysis of the memory kernel function of the Onsager coefficient identifies two characteristic relaxation times, which are both smaller than the Rouse time, a signature suggesting that memory effects are closely related to short-time segmental motions. By defining two types of time averages and comparing their asymptotic behaviors at the long-time limit, we establish connections linking the history-dependent Onsager coefficient, the instantaneous Onsager coefficient, and the memory-free one, which provide a theoretical foundation for quantitatively evaluating the reliability of various DDFT implementations. Our data-driven framework is easily extensible to other different systems, combining different particle-based simulations and continuum field-based DDFT schemes, thereby providing a useful framework for developing structure–property correlations in complex polymer systems.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"24 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189548","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}

{"title":"Effects of Isohexide Stereochemistry on Vinylogous Urethane Covalent Adaptable Networks","authors":"Noé Fanjul-Mosteirín, Karin Odelius","doi":"10.1021/acs.macromol.5c00270","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00270","url":null,"abstract":"The starch-derived isohexides, with their unique structures of two fused tetrahydrofuran rings in a cis conformation, have been exploited to prepare covalent adaptable networks (CANs) and to tailor and understand their structure–property relationships, in pursuit of replacing oil-based thermosets. Here, dynamicity was achieved through vinylogous urethane chemistry, rigidity via the use of the starch-derived isomeric building blocks isosorbide, isomannide, and isoidide, and flexibility through the amines utilized. Similar to what is known for thermoplastics, depending on the isomer chosen, thermal stability and mechanical properties could be tailored to some extent. The distance between cross-links was ruled by the amines employed, and when this distance was long enough to allow sufficient chain mobility, stereochemical effects on mechanical performance were observed. The CAN structures all display thermoset properties, and as a consequence of the incorporated dynamic bonds, they were mechanically reprocessable. Based on the CANs structural design, i.e., isohexide isomer and amine structure, tensile strengths (σ_b) ranging from 1.57 to 19.1 MPa, glass transition temperatures (T_g) ranging from 20 to 114 °C, and thermal stabilities (T_d,5%) between 200 and 305 °C were achievable. Mechanical reprocessing was proven, and no mechanical performance decay was observed after two reprocessing cycles. This provides important information on the structure–property relationship of CANs from starch-derived building blocks, and consequently, how material properties can be tailored depending on the targeted application.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"24 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189532","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}

{"title":"Quantitative Correlation of Single-Molecule Mechanical Behavior with the Yield Stress of Polymer Fibers","authors":"Xiaoye Zhang, Shengjie Lu, Honglin Zhang, Yu Song, Wenke Zhang","doi":"10.1021/acs.macromol.5c01683","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01683","url":null,"abstract":"A quantitative correlation between single-molecule and macroscopic mechanical properties is crucial for rationally improving the performance and designing polymer materials. However, it remains challenging due to the complexity of the material systems and the lack of suitable methods for characterizing single-molecule structures and mechanics in real materials. Here, we report a quantitative correlation between the single-molecule mechanics of the tie chains and the macroscopic mechanical properties of polycaprolactone and polyethylene (PE) fibers. The density and stress of tie chains were quantified by using atomic force microscopy-based single-molecule force spectroscopy (SMFS) to pull single polymer chains out of the fibers along the fiber axis. The SMFS-predicted maximum yield stress (σ_SMFS) was comparable to the tensile yield stress (σ_y) of fibers, with the utilization of tie chains (σ_y/σ_SMFS) in PE fiber reaching 96%. Moreover, this quantitative correlation was validated by the dependence of the density and utilization of tie chains on the stretching orientation. Finally, we illustrate a subnanometer-level length adjustment mechanism of tie chain, which explains the extremely high utilization of tie chain in PE fiber and further proves our quantitative correlation.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"99 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183037","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}

{"title":"Robust Artificial Spider Silk via Synergistic Cross-Linking of Slide-Ring and Covalent Bonds","authors":"Guangkai Mei, Zihao Su, Ning Liu, Junli Qu, Xiao Liu, Dong Qian, Xiang Zhou, Zunfeng Liu","doi":"10.1021/acs.macromol.5c02101","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c02101","url":null,"abstract":"Inspired by the structure of spider silk, the introduction of slide-ring molecules into covalent networks to construct double cross-linked networks (DCNs) has become an effective strategy for preparing robust polymer artificial spider silk. However, the complex interplay between the two cross-linking modes poses significant challenges for elucidating the molecular mechanisms underlying mechanical enhancement and hinders the precise design and fabrication of robust artificial silks. Here, we engineered robust artificial spider silk fibers based on DCNs and employed coarse-grained molecular dynamics (CGMD) simulations to establish quantitative models linking the network architecture to macroscopic mechanical properties. The models reveal that slide-ring-only networks suffer from ring aggregation and chain slippage under strain, which leads the multifolded axis chains to straighten and unfold, ultimately forming highly oriented structures. In contrast, DCNs utilize covalent anchors to regulate the ring mobility, stabilize multifolded chain structures, and balance energy dissipation with mechanical integrity. These molecular-level insights are supported by experiments. By tuning the slide-ring cross-linking fraction and introducing Zr⁴⁺ ions as dynamic supramolecular regulators, we achieved highly aligned nanofibers with both exceptional tensile strength (1.18 GPa) and toughness (135 MJ m^–3). The synergy between dynamic and permanent cross-links enables efficient stress redistribution and crack resistance. This work provides inspiration for the design of high-performance fiber materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"15 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145154059","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}

{"title":"Electrochemical C–H Phosphonylation of Dissolved Conjugated Polymers via Direct Electron Transfer at the Electrode","authors":"Kohei Taniguchi, Kosuke Sato, Shinsuke Inagi","doi":"10.1021/acs.macromol.5c01783","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01783","url":null,"abstract":"π-Conjugated polymers (CPs) exhibit attractive optoelectronic properties conferred by an extended π-conjugation system along their main chains. CPs containing polar phosphonate groups have attracted special interest because their exceptional affinity to metal ions and electrodes can be exploited in electrochemical devices. A favorable strategy for postfunctionalizing CPs with phosphonate groups is electrochemical phosphonylation, which requires only a simple protocol under mild reaction conditions. However, this established method requires a CP film for the electrolytic process. A postfunctionalization method based on the conventional electrolysis of CPs in solution is expected to improve the versatility and scalability of electrochemical phosphonylation. Herein, we demonstrate that CPs dissolved in an electrolyte can be electrochemically phosphonylated via direct electron transfer at the anode. In particular, we show the quantitative phosphonylation of poly(9,9-dioctylfluorene) (PFO) at low current densities, despite the small diffusion coefficient of PFO. Stirring-induced convection facilitated polymer diffusion, thereby improving the efficiency of electrochemical PFO phosphonylation. Moreover, the degree of functionalization could be precisely controlled by adjusting the amount of passed charge. Interestingly, a moderate functionalization degree improved the fluorescence quantum yield to 0.82 in phosphonylated PFO and the reaction proceeded from various trialkyl phosphites. Finally, the reaction mechanism of anodic phosphonylation was determined through density functional theory calculations.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"41 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140709","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}

{"title":"Development of Polyolefin Elastomers with Distinct Dual Long-Chain Branch Structures","authors":"Bangban Zhu, Haitao Wang, Kan Liu, Minghao Sun, Zhenjia Shi, Shuo Wang, Xingfen Huang, Shengbin Shi, Jieyuan Zheng, Xuan Yang, Pingwei Liu, Wen-Jun Wang","doi":"10.1021/acs.macromol.5c01900","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01900","url":null,"abstract":"Long-chain branched (LCB) structures significantly impact the processability and mechanical performance of polyolefin materials. Comb-branched polyolefin elastomer (CPOE) represents an emerging class of polyolefin thermoplastic elastomers composed of an amorphous ethylene/1-octene copolymer backbone and crystalline polyethylene (PE) LCBs (T-type). While CPOEs exhibit higher melting points and improved thermal stability compared to conventional polyolefin elastomers, achieving both high mechanical strength and excellent elastic recovery remains a key challenge. In this study, a second LCB structure was strategically introduced into CPOEs to develop a dual-branched polyolefin elastomer (DPOE). In addition to the existing crystalline T-type LCBs, which act as reversible physical cross-linking sites, covalently bonded H-type LCBs were generated through the incorporation of 1,7-octadiene. The resulting DPOEs possessed 0.5–0.6 T-type LCBs and 0.5–1.6 H-type LCBs per polymer chain, forming an integrated dual cross-linking network. This dual-LCB design led to a remarkable enhancement in mechanical properties and thermal performance. Compared to CPOEs, the DPOEs exhibited an increase in tensile strengths from 9.4 to 16.6 MPa, elongations at break from 975% to 1085%, toughness from 70.1 MJ/m³ to 105 MJ/m³, and elastic recoveries from 65.8% to 73.7%. Furthermore, the DPOEs maintained a storage modulus plateau of 0.2–0.3 MPa across the 150–200 °C range. Notably, the materials also showed outstanding reprocessability, retaining up to 96% of their original mechanical strengths and nearly unchanged elongations at break after five hot-pressing cycles. The introduction of dual LCBs offers a powerful design strategy for producing high-performance, thermally stable, and reprocessable polyolefin thermoplastic elastomers, expanding their potential for advanced industrial applications.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"15 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145140712","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}