Macromolecules最新文献

{"title":"Solvent-Free Superionic Polymer Conductors from a Bicontinuous Network Nanostructure","authors":"Shuqi Dai, Jinyi Cui, Xueying Yuan, Yongmei Zhu, Jinxin Xie, Xing-Han Li, Zhiwei Yan, Rongchun Zhang, Weijiang Xue, Xian Kong, Mingjun Huang","doi":"10.1021/acs.macromol.5c00294","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00294","url":null,"abstract":"In traditional ion conducting polymers, the lithium-ion transport is strongly coupled with segmental motion of a polymer chain. The resulted severe weakness of room-temperature ion conductivity and mechanical strength necessitates the development of superionic conductors, which decouple lithium-ion conduction from polymer segmental relaxation. Here, we demonstrate a simple and efficient superionic lithium conductor system based on polyacrylonitrile (PAN)-grafted ferroelectric poly(vinylidene fluoride) (PVDF), i.e., PVDF-<i>g</i>-PAN. A bicontinuous network nanostructure is constructed through the microphase segregation. The ferroelectric PVDF network not only presents a high dielectric constant, facilitating dissociation of high-concentration lithium salts, but also strongly interacts with fluorinated anions to enhance the lithium transference number (&gt;0.6). The PAN-rich network with abundant polar nitrile groups and high glass transition temperature serves as the Li⁺ hopping channels, enabling high ion conductivity (5.8 × 10^–4 S cm^–1, 30 °C), low activation energy (0.21 eV), as well as excellent mechanical strength (&gt;200 MPa). In particular, a nearly solvent-free condition is realized, enabling long-term stability of ion conducting performance.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"12 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144320319","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":"Tunable Electric Double-Layer Capacitor Performance through Engineered Charge Patterns in Polyelectrolytes","authors":"Yan Sui, Tingting Yin, Zixiao Yang, Yichun Zhao, Xiaoyu Kong, Dongluo Wu, Jiajia Zhou, Xiupeng Chen, Xian Kong","doi":"10.1021/acs.macromol.5c00595","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00595","url":null,"abstract":"Understanding how charge fraction and sequence in polyelectrolytes (PEs) affect electric double-layer capacitors (EDLCs) is crucial for optimizing energy storage devices. We employed antisymmetric PEs composed of polycations and polyanions with identical charge patterns, eliminating counterion effects and focusing on intrinsic PE–electrode interactions. Our simulations revealed that increasing the charge fraction enhances differential capacitance due to more charged species facilitating efficient charge storage. Block-patterned PEs, where charged beads are grouped along the polymer chain, exhibited higher integral capacitance than regular-patterned PEs and simple electrolytes but resulted in slower charging rates due to substantial conformational adjustments during adsorption. Both types of PEs promoted enhanced overscreening, increasing the charge accumulation near the electrode surface. These findings highlight the significant impact of the charge fraction and sequence on the EDLC performance. Careful selection of PE charge patterns can thus tailor energy storage capacities and charging rates to meet specific application needs.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"38 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144320320","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":"Improved Electromechanical Performance of Dielectric Elastomers via Constructing an All-Organic Composite Structure","authors":"Chuying Zhang, Haotong Guo, Na Zhang, Liming Jin, Jinbo Bai, Hang Zhao","doi":"10.1021/acs.macromol.5c00971","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00971","url":null,"abstract":"Dielectric elastomers (DEs) can be deformed in response to an electric field. However, an excellent electro-actuated strain of DEs is usually achieved at high applied voltages, which severely limits their application range. Moreover, flexible DEs are susceptible to electromechanical breakdown, which directly affects their operational life. Herein, a novel all-organic DE composite was designed. First, isooctyl 3-mercaptopropionate (IOMP)-grafted methyl vinyl silicone (MVQ) was prepared to enhance the polarization and reduce cross-link density of macromolecular chains. Furthermore, 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA) was incorporated into the MVQ–IOMP matrix. The positively charged NTCDA can capture free charges through strong electrostatic interaction, thus enhancing the breakdown strength of DEs. Ultimately, a 1 wt % NTCDA/MVQ–IOMP_0.75 DE composite obtains an extremal actuated strain of 52.9% under 45.2 V/μm and a maximum actuated strain of 37.3% under its safe electric field (36.1 V/μm). Consequently, this work provides a feasible way for preparing advanced DE composites.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"5 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144311772","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":"Cationic Dithiocarbamate for Efficient Blue Light-Controlled Photoiniferter Polymerization","authors":"Ziya Qing, Wenxin Wang, Ruoyu Li, Zesheng An","doi":"10.1021/acs.macromol.5c00174","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00174","url":null,"abstract":"<i>N</i>-phenyl-<i>N-</i>pyridin-1-ium dithiocarbamate was developed as a versatile iniferter for blue light-controlled radical polymerization. Tunable solubility in both water and various organic solvents was achieved through counterion exchange (Br^– or PF₆^–). UV–visible absorption spectroscopy revealed strong blue light absorption. Kinetic studies for the photoiniferter polymerization of various monomers conducted using the dithiocarbamate in comparison with other iniferters revealed a combination of faster polymerization rates, shorter induction periods, and good control over molecular weights and molecular weight distributions. Electron paramagnetic resonance (EPR) studies demonstrated a faster photolysis rate for the dithiocarbamate compared to a trithiocarbonate iniferter. Photoiniferter polymerizations were conducted for <i>N</i>,<i>N</i>-dimethylacrylamide, <i>N</i>-acryloylmorpholine, methyl acrylate, poly(ethylene glycol) methyl ether acrylate (<i>M</i>_n = 480 g mol^–1), and <i>N</i>,<i>N</i>-dimethyl lactamide acrylate in various solvents using the dithiocarbamate iniferter, yielding the corresponding homopolymers with controlled molecular weights (up to an <i>M</i>_n of 1316.8 kg mol^–1) and narrow dispersities. High end-group fidelity was confirmed by ¹H NMR spectroscopy and matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, enabling one-pot synthesis of well-defined diblock copolymers. Combining rapid kinetics, solvent versatility, and no requirement for acid additives, this system offers an accessible platform for precision polymer synthesis under mild, visible-light conditions.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"45 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144311770","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":"Strong and Ultra-Tough Hydrogel with Hierarchical Cross-Linking Network Architecture Constructed by a Hyperbranched Topological Structure","authors":"Ying Zhu, Hanjing Zhang, Qinwen Tan, Yangfei Wu, Mengting Du, Nikos Hadjichristidis, Yu Jiang, Daohong Zhang","doi":"10.1021/acs.macromol.5c00513","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00513","url":null,"abstract":"Natural biological tissues such as jellyfish integrate hierarchical architectures with multifunctionality (e.g., bioluminescence, mechanical resilience, and responsiveness), yet replicating such synergy in synthetic hydrogels remains a significant challenge. Here, we present a bioinspired hydrogel engineer that employs a hyperbranched macro-cross-linker as a topological regulator to precisely manipulate the hierarchical cross-linking network architecture. Compared to the linear macro-cross-linker, the introduction of a hyperbranched topological structure has endowed the hydrogel with excellent mechanical properties. By systematically tuning branching parameters (DB and <i>S</i>_n), we further achieve simultaneous modulation of both the microphase separation morphology and multistage cross-linking networks. With moderate DB and <i>S</i>_n, the hydrogel exhibits an optimal hierarchical structure and the most uniform microphase separation, achieving the integration of excellent mechanical performance, remarkable unconventional fluorescence emission, and notable conductivity. Furthermore, the hydrogel demonstrates highly sensitive dual optical–electrical responsive behaviors when used as a strain sensor. This strategy provides a universal platform for designing hierarchical hydrogels with programmable functionality, offering promising material for advanced applications in bioelectronics and soft robotics.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"45 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144311771","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":"Phase Behavior of Reversibly Bonding Polymer Blends","authors":"Christopher Balzer, Puck Springintveld, Glenn H. Fredrickson","doi":"10.1021/acs.macromol.5c01173","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c01173","url":null,"abstract":"Blending polymers is a versatile strategy for creating materials with tailored properties, but controlling the phase behavior of polymer blends remains a central challenge. Functionalization with sparse, associative chemical groups is a powerful way to shift phase behavior without changing individual component properties. We develop a field-theoretic model for heteroassociating polymer blends using the coherent states formalism, enabling an exact treatment of reversible bonding while avoiding explicit enumeration of polymer topologies. This framework captures the full distribution of supramolecular species, including higher-order branching and large clusters, and reveals how correlations between association sites of multifunctional polymers govern thermodynamic behavior across length scales. Using the random phase approximation, we identify conditions for macrophase separation and microphase ordering, and uncover a new motif for microphase separation in which bond density, rather than species density, exhibits spatial variations. These results unify and extend existing theories of reversibly bonding polymers, including phenomena such as gelation, and establish a foundation for designing compatibilizers through polymer architecture and sequence-level control of reversible interactions.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"15 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144320321","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":"Synthesis of Compact Single-Chain Nanoparticles in Concentrated Solutions","authors":"Kairu Qu, Zhenzhong Yang","doi":"10.1021/acs.macromol.5c00611","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00611","url":null,"abstract":"Although a large family of covalently cross-linked robust single-chain nanoparticles (SCNPs) have been extensively synthesized, they are sparsely cross-linked, lacking precision control of the compactness. Herein, we propose a facile method to achieve robust SCNPs with tunable compactness by covalent cross-linking of the parent dynamic SCNPs. As proof of the concept, the dynamic SCNPs are large-scale synthesized at 200 mg/mL by the electrostatics-mediated intramolecular physical cross-linking of poly(<i>N</i>,<i>N</i>-dimethylaminoethyl methacrylate) (PDMAEMA)-based polymers via amino/acid-specific interactions. The compactness of the dynamic SCNPs is greatly tunable from sparsely cross-linked to the globular state with scaling parameters from 0.57 to 0.34 by altering the cross-linking degree and spacer length of the cross-linker. The robust SCNPs with tunable compactness are derived by subsequent covalent cross-linking of the dynamic SCNPs. The SCNPs are featured with functional microdomains distinctly compartmentalized by using functional agents and preferential growth of functional materials thereby.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"14 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144311773","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":"Novel Insights into Solution Electrospinning for Nanofibers","authors":"Chi Wang, Pin-Hsien Lu, Yin-Chuan Kuo, Chih-Hsien Kuo, Hsin-Yi Lai, Shao-Hua Wu, Takeji Hashimoto","doi":"10.1021/acs.macromol.5c00703","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00703","url":null,"abstract":"To understand how nanofibers are formed by solution electrospinning, an in situ observation of the fluid flow is essential. In this study, the flow behavior of charged fluids from the Taylor cone, straight jet part, until whipping (or spiral) jet part along the spinline is explored via particle image velocimetry, light scattering, and high-speed videography, respectively. The results of light scattering reveal that the stretching rate in the straight jet exceeds the intrinsic rates of polymer relaxation in the fluid, derived from the dynamic rheological measurement, supporting the hypothesis of flow-induced phase separation and the resultant evolution of the dissipative structures, the so-called “string” structures, in the straight jet section. Using liquid nitrogen to collect the straight jet followed by freeze-drying, assembled strings with various widths are validated. Moreover, dynamic vortex flow is observed in the Taylor cone using particle image velocimetry, likely generating a swirling flow in the cone apex. The vorticity of the swirl is increased after passing the cone-jet transition zone, at which the electric field is the highest. Thereafter, the enhanced swirl gradually decays (or releases its imposed torsion) during its propagation along the straight jet via a jet twist. The straight jet with internal swirl is considered as the precursor of the spiral jet, given that the preimposed torsion in the straight jet is not completely relaxed at the straight jet end. Using high-speed videography, a transition of the handedness of the spiral jet, rotating either clockwise or counterclockwise, is repeatedly observed in a single spinning line, suggesting the intermittent entry of the swirl with different handedness in the cone apex. Thus, the downstream spiral jet is relevant to the upstream entry flow at the cone apex; this phenomenon resembles the classic extrusion instability. Helical fibers (or coils) are observed on the ground collector, as the residual torsion in the spiral jet is not fully released after solvent evaporation in the spinning line of the spun fiber. Our work shows that important external flow fields are applied to semidilute solutions through the electrospinning process, which self-organizes nanofibers as ordered structures from dissipative structures through thermal concentration fluctuations along the spinning line, starting from the needle tip to the whipping jet.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"603 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144311775","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":"An In Situ Method for Deciphering Nanomechanical Behavior in Elastomer Nanocomposites under Large Deformation","authors":"Xiaobin Liang, Haonan Liu, Naruto Maeda, Masato Suzuki, Makiko Ito, Naoya Amino, Masataka Koishi, Ken Nakajima","doi":"10.1021/acs.macromol.5c00844","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00844","url":null,"abstract":"The optimization of mechanical properties and the expansion of applications for elastomers such as rubber and hydrogels have been longstanding focal points in materials science research. This study investigates the mechanical behavior and deformation mechanisms of elastomer nanocomposites under large strains, focusing on the reinforcing effect of nanofillers such as carbon black (CB) and carbon nanotube (CNT). Using a nanoscale visualization method based on atomic force microscopy (AFM) integrated with a microprecision-controlled uniaxial tensile device, we achieved in situ tracking of microscopic deformation behavior and stress distribution within a 200% strain range. The study reveals that the stress transmission and distribution mechanisms in nanocomposites vary significantly with the type and morphology of the nanofillers. CB composites form stress chains under strain, which interact with CB fillers to create a stress network structure, leading to significant reinforcement. In contrast, CNT composites exhibit a different mechanism due to their high aspect ratio and orientation behavior. These findings provide crucial insights into the design of nanocomposite rubber materials with tailored mechanical properties, contributing to advancements in biosensors, carbon-neutral technologies, and aerospace engineering.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"35 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144311776","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":"Interfacial Dynamics and Mechanical Properties of Substrate-Supported [c2]Daisy Chain Networks","authors":"Yang Wang, Guoquan Liu, Zhaoming Zhang, Andrea Giuntoli, Xuzhou Yan","doi":"10.1021/acs.macromol.5c00619","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00619","url":null,"abstract":"Mechanically interlocked networks (MINs) comprise molecular components linked through mechanical bonds, imposing topological constraints that prevent fragment separation. Despite extensive experimental works on this intriguing material, theoretical investigations remain limited. Herein, we employ coarse-grained molecular dynamics simulations to explore the structure, interfacial dynamics, ring sliding, and mechanical properties of substrate-supported MINs thin films composed of [<i>c</i>2]daisy chains, where the effects of potential sliding distances (<i>n</i>), cross-linking degree (<i>c</i>), interfacial cohesive strength (ϵ_ps), and temperatures (<i>T</i>) are systematically explored. Our results show that stronger dynamic confinement occurs near the substrate with increasing ϵ_ps, particularly at lower <i>T</i>. Conversely, lower ϵ_ps (≤0.5) enhances the dynamics of the [<i>c</i>2]daisy chain near the substrate, resembling free-surface behavior. Interestingly, ring molecules display slower dynamics than axle chains, whose mobility strongly depends on proximity to the binding site, consistent with previous experimental studies. Conformational behavior remains largely unaffected by variations in ϵ_ps, <i>T</i>, and <i>c</i>, while an increase in <i>n</i> slightly enhances chain dynamics, increasing the radius of gyration (<i>R</i>_g). Pull-out tests reveal three stages in explaining the ring sliding mechanism. Initially, the ring tilts on the axle under tension without dissociation due to strong binding interactions. Subsequently, the ring dissociates from the binding site, leading to a rapid increase in sliding distance. Finally, the sliding distance reaches a plateau that matches the <i>n</i> value of the model. The durations of the latter two stages are significantly influenced by <i>c</i>. Higher <i>c</i> promotes crazing fiber formation, triggering an earlier onset of the second sliding stage, and increasing plateau stress during pull-out. These findings offer molecular-level insights into [<i>c</i>2]daisy chain MIN behavior, providing a foundation for future research on diverse MIN architectures and their applications in smart and adaptive materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"24 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144311774","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}