Macromolecular Rapid Communications最新文献

{"title":"Polymerization-Induced Micelle Gelation.","authors":"Liangwei Lu, Shuxiao Wang, Wei Hong, Jiaping Lin, Liquan Wang","doi":"10.1002/marc.202500622","DOIUrl":"https://doi.org/10.1002/marc.202500622","url":null,"abstract":"<p><p>Self-assembly of polymer micelles offers a novel pathway to supramolecular structures such as 1D nanowires, yet gelation behavior remains underexplored. We demonstrated a universal copolymerization strategy using acrylic acid and methyl methacrylate to fabricate micellar hydrogels. Initiator concentration critically regulates gelation, i.e., low concentrations enable isolated micelle polymerization into compact 3D networks at the gelation threshold. Dissipative particle dynamics simulations corroborate experimental findings, revealing that multiblock copolymer formation at low initiator levels facilitates inter-micellar bridging via alternating hydrophilic/hydrophobic chains, while high concentrations yield diblock copolymers limited to isolated micelles. This facile approach enables scalable production of hydrogels for broad applications.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00622"},"PeriodicalIF":4.3,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145197739","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Thermodynamic Labeling Enables CO₂ Prediction in Polymers of Intrinsic Microporosity under Small Data Constraints.","authors":"Johnathan W Campbell, Ashley P DeRegis, Jeffrey A Laub, David S Sholl, Konstantinos D Vogiatzis","doi":"10.1002/marc.202500490","DOIUrl":"https://doi.org/10.1002/marc.202500490","url":null,"abstract":"<p><p>Porous polymers, particularly polymers of intrinsic microporosity (PIMs), combine high surface areas with tunable functionalities, positioning them as promising materials for post-combustion CO₂ capture technologies. A key physical parameter of these materials is the isosteric heat of adsorption (Q_st), which quantifies the interaction strength between CO₂ molecules and the polymer framework. In this work, we demonstrate that data-driven models constructed from computationally determined physicochemical descriptors can accurately predict Q_st at room temperature using a modestly sized dataset of 75 PIMs. Among the multitude of machine learning models evaluated, Kernel Ridge Regression (KRR) utilizing the radial basis function (RBF) yielded notable training and testing coefficients of determination (R² scores) of 0.9854 and 0.9653, respectively. Additionally, an ensemble model was constructed using the KRR RBF, Lasso Regression, and XGBoost, achieving an average training R² score of 0.9844 and a testing score of 0.9651. By optimizing model parameters through Bayesian methods and interpreting feature importance using SHAP analysis, we identified the molecular characteristics that most strongly influence the prediction of CO₂-PIMs isosteric heats of adsorption. Using a Lasso model, we screened a synthetic PIM parameter space by varying six thermochemical descriptors, revealing density as the most influential factor and identifying optimal combinations to enhance predicted isosteric heats of adsorption. These results demonstrate that accurate predictive workflows can be developed using relatively small datasets for designing polymeric adsorbents by identifying key molecular descriptors that correlate with the isosteric heat of adsorption. Overall, this adaptable methodology can be extended to future gas-separation challenges, helping pave the way for faster discovery of advanced polymeric membranes for capturing CO₂.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00490"},"PeriodicalIF":4.3,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145190489","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Impact of Metal Coordination on the Structures and Dynamics of Ethyl Acrylate-Vinylimidazole Copolymers.","authors":"Kun Yang, Yuling Liang, Peizhi Zhao, Yixiang Yan, Li Peng, Xianbo Huang, Rongchun Zhang","doi":"10.1002/marc.202500601","DOIUrl":"https://doi.org/10.1002/marc.202500601","url":null,"abstract":"<p><p>The integration of weak sacrificial bonds into the polymer networks has become a universal approach for enhancing the mechanical properties of polymers. Particularly, the presence of non-covalent associative interactions leads to significant changes in polymer dynamics and viscoelastic behaviors. In this study, we report a high-performance metallo-supramolecular elastomer based on metal-imidazole coordination. Different metal ions, including Cu²⁺, Co²⁺, and Zn²⁺, were incorporated into a random copolymer composed of ethyl acrylate (EA) and 1-vinylimidazole (VI), resulting in dramatic variation in mechanical and viscoelastic properties due to differences in metal-coordination strength. High-resolution 2D ¹H double-quantum/single-quantum (DQ/SQ) NMR spectroscopy directly reveals the formation of metal-coordination in the polymer materials and shows that metal-coordination leads to enhanced structural and dynamic heterogeneity. Specifically, both local segmental motions and terminal relaxation of metallo-supramolecular elastomer are slowed down by the metal-coordination. This study provides detailed molecular-level insights into the structure and dynamics of polymer networks with varying metal-coordination strengths, providing great potential for the rational design of high-performance metallo-supramolecular polymers.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00601"},"PeriodicalIF":4.3,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145190538","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Building From the Ground Up: A Procedural Guide to Locally Controlling Bond Exchange Kinetics in Dynamic Thiol-Thioester Networks.","authors":"Roman Korotkov, John Vincent Tumaneng, Roberta Bongiovanni, Sara Dalle Vacche, Elisabeth Rossegger, Sandra Schlögl","doi":"10.1002/marc.202500654","DOIUrl":"https://doi.org/10.1002/marc.202500654","url":null,"abstract":"<p><p>Covalent adaptable networks (CANs) are a new class of polymers possessing the structural robustness of classical thermosets and stimuli-dependent malleability of thermoplastics, imparting them with repairability, reprocessability, and recyclability potential. These CANs can even be tailored to have spatially controllable properties and enhanced functionality; however, the introduction of additional reactive moieties leads to inadvertent side reactions and deterioration of the desired performance. Herein, we present a comprehensive approach to the optimization of locally controllable CANs, relying on base catalyzed thiol-thioester exchange reactions. The network is formed by visible light (405/450 nm) induced radical thiol-ene polymerization, whilst local deactivation of the dynamic exchange reaction is achieved by neutralizing the basic catalyst with a photoacid generated upon UV-light (365 nm) exposure. The intricate interactions between the resin components were studied, and the factors affecting the network performance were investigated to provide a detailed account of the development process, from the rational selection of initial components to the systematic optimization of a locally controlled, photoswitchable CAN. Finally, its on-demand tunability is demonstrated by surface- and bulk shape reconfiguration through heat-assisted processes.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00654"},"PeriodicalIF":4.3,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145190501","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Uncovering Key Characteristics of Antibacterial Peptides through Machine Learning.","authors":"Jooyoung Roh, Cyrille Boyer, Priyank V Kumar","doi":"10.1002/marc.202500583","DOIUrl":"https://doi.org/10.1002/marc.202500583","url":null,"abstract":"<p><p>Antimicrobial peptides (AMPs) have emerged as promising alternatives to traditional antibiotics in addressing the growing threat of multi-drug-resistant (MDR) bacteria-a crisis that could lead to millions of deaths over the next three decades if left unaddressed. While the general role of cationic and hydrophobic interactions in AMP-mediated bacterial killing is well established, the distinctions between structural characteristics of AMPs targeting different types of bacteria remain underexplored. To address this issue and streamline the design of potent AMPs depending on the bacterial structure, machine learning (ML) models were employed on AMPs targeting Gram-negative bacteria (Pseudomonas aeruginosa PAO1), Gram-positive bacteria (Staphylococcus aureus ATCC 29213), and mycobacteria (Mycobacterium tuberculosis H37Rv and Mycobacterium smegmatis mc² 155) to derive important features that determine antimicrobial efficacy. The Random Forest models mainly reveal that AMPs with a cLogP of less than -6 and a net-charge limited to +4 with variations of the hydrophobic composition in between 20%-50% (20%-40% against P. aeruginosa PAO1, 30%-50% against S. aureus ATCC 29213, 35%-45% against M. tuberculosis H37Rv and M. smegmatis mc² 155) and variations of the cationic composition in between 10%-40% (10%-20% against P. aeruginosa PAO1, 30%-40% against S. aureus ATCC 29213, 10%-30% against M. tuberculosis H37Rv and M. smegmatis mc² 155) predicts significant antibacterial activity. The feature characteristics of the three bacterial types may directly relate to their distinct cell envelope structures and aid in mode of action postulation. This work demonstrates how ML can effectively inform AMP design by accounting for microbial structural differences and underscores its broader potential in customizing peptides for specific bacterial strains.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00583"},"PeriodicalIF":4.3,"publicationDate":"2025-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145184380","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multifunctional Mussel-Inspired Hydrogels and Films Formed via Catechol-VO₂ Nanoparticle Coordination.","authors":"Mostafa Rammal, Matthew J Harrington","doi":"10.1002/marc.202500587","DOIUrl":"https://doi.org/10.1002/marc.202500587","url":null,"abstract":"<p><p>Marine mussels utilize DOPA-V metal coordination bonds as dynamic cross-links to fabricate tough and self-healing coatings and glues. Inspired by mussels, researchers have harnessed DOPA-metal coordination to create dynamic and mechanically responsive polymeric materials. Here, we harness the robust DOPA-V interactions observed in mussels combined with the temperature-responsive properties of vanadium dioxide (VO₂) to develop a room-temperature process to produce thermochromic VO₂ hydrogels and films. 4-arm polyethylene glycol (PEG) polymers functionalized with DOPA-catechol moieties were mixed with VO₂ nanoparticles in solution. Raising pH led to formation of hydrogels, while spin coating enabled processing into thin films. Hydrogels possessed mechanically tunable viscoelasticity and self-healing response. Furthermore, dried free-standing films were highly flexible and exhibited plastic deformation with extensibilities of 200% and beyond, while still retaining the thermochromic properties of the nanoparticles. The facile fabrication method and the resulting versatile mechanical response combined with thermochromic properties are promising for future development VO₂-polymer composite materials.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00587"},"PeriodicalIF":4.3,"publicationDate":"2025-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145181684","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multimodal Machine Learning with 3D-Weighted-Matrix Encoding for High-Throughput Design of High-Performance Polyurethanes.","authors":"Shushuai Zhou, Wanchen Zhao, Zilong Wan, Haoke Qiu, Xianbo Huang, Zhao-Yan Sun","doi":"10.1002/marc.202500471","DOIUrl":"https://doi.org/10.1002/marc.202500471","url":null,"abstract":"<p><p>Polyurethanes (PUs) are ubiquitous in our daily life, while facing fundamental challenges in designing materials with targeted mechanical properties due to their inherent structural complexity. To address this, we developed an extensible high-throughput screening framework that combines machine learning, multimodal feature engineering, and feature fusion strategy to enable the mechanical property prediction of PU materials. Specifically, an effective 3D-Weighted-Matrix encoding method was proposed to represent polyurethane monomers, indicating better performance than conventional molecular descriptors (23% improvement in feature discriminability). Synthesis process parameters were also digitized through logic-based encoding and fused with structural features (including chemical structure representations via 3D-Weighted-Matrix and molecular descriptors as well as synthesis process information) via an early fusion architecture, yielding a multimodal deep learning model capable of concurrent prediction of Young's modulus, tensile strength, and elongation at break with mean coefficient of determination ( <math> <semantics><msup><mi>R</mi> <mn>2</mn></msup> <annotation>${rm R}^{2}$</annotation></semantics> </math> ) values exceeding 0.86. With this model, we then performed combinatorial screening of more than 150 million molecular and process combinations, identifying optimal candidates that promote various mechanical performance metrics. This work enhances our comprehension of the intrinsic structure - property correlations in PU and introduces a powerful computational framework for the accelerated development of high - performance polyurethane materials.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00471"},"PeriodicalIF":4.3,"publicationDate":"2025-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145181734","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fabrication of Fluorinated Tannic Acid-Modified Waterborne Epoxy Resin Coatings and Investigation of Their Long-Term Corrosion Resistance.","authors":"Xuan Liu, Rui Yang, Xiaofeng Han, Hao Xing, Muhan Li, Chao Wang, Mingxi Wang, Dandan Wang, Yuan Li, Yang Dai, Xiaojuan Lai","doi":"10.1002/marc.202500636","DOIUrl":"https://doi.org/10.1002/marc.202500636","url":null,"abstract":"<p><p>Waterborne epoxy resin (WEP) has gained attention for its low volatile organic compound (VOC) emissions, making it a key focus in eco-friendly coatings. However, its corrosion resistance still lags behind that of traditional solvent-based coatings. Tannic acid (TA), a natural polyphenolic compound, shows strong metal chelating ability and potential for corrosion protection. Yet, its high hydrophilicity limits its use in coatings. Herein, fluorinated tannic acid (F_xTA) with different degrees of fluorination was synthesized by grafting polyhexafluorobutyl acrylate (PHFBA) onto tannic acid and was introduced into the WEP matrix as a functional filler to enhance its anti-corrosion performance. Electrochemical tests demonstrated that the F₃TA filler in the F_xTA/WEP composite coatings exhibited the most superior performance. When the filling amount of F₃TA was 4.9 mL, the contact angle of the 4.9-F₃TA/WEP composite coating increased to 86.42°, and the water absorption rate decreased by approximately 52.37%. Moreover, this composite coating maintained a basic constancy in hardness and adhesion while having a tensile strength of 2.51 MPa and an elongation at break of 77.80%, demonstrating excellent mechanical properties. The electrochemical impedance modulus of the 4.9-F₃TA/WEP coating is 2.13 × 10⁸ Ω·cm², and it maintains a high value of 2.0⁷ × 10⁷ Ω·cm² even after 20 days of salt spray exposure, demonstrating its excellent corrosion resistance. This study offers novel insights into the functional modification of natural polyphenolic compounds and introduces an environmentally friendly coating system capable of providing excellent long-term corrosion protection.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00636"},"PeriodicalIF":4.3,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145172246","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Light and Temperature Dual-Responsive Liquid Marbles Stabilized with Azobenzene-Modified Poly(N-Isopropyl Acrylamide).","authors":"Yunhui Wen, Yuzheng Luo, Yang Yang, Yuanting Qiao, Chen Zhang, Shaowei Shi","doi":"10.1002/marc.202500543","DOIUrl":"https://doi.org/10.1002/marc.202500543","url":null,"abstract":"<p><p>Liquid marbles have garnered significant attention as versatile platforms for microreactor technologies, owing to their ease of handling and programmable fluidic operations, particularly through stimuli-triggered coalescence behavior that enables spatiotemporally controlled reagent mixing. However, current systems often rely on operationally complex methods. Meanwhile, the capability for multi-stimulus responsiveness can expand the application range of liquid marbles and enhance their adaptability to complex environments. This study presents a light- and temperature-responsive liquid marble by encapsulating a water droplet with azobenzene-modified poly(N-isopropyl acrylamide) (Azo-PNIPAM). The addition of hydrophobic groups enables the precise regulation of the lower critical solution temperature (LCST) of Azo-PNIPAM, thereby developing a strategy for accurately controlling the stability of liquid marbles and addressing the gap in stability modulation of liquid marbles using two classic stimulus-responsive components, PNIPAM and azobenzene. The liquid marbles can disintegrate under UV light irradiation or at low temperature due to the increased hydrophilicity of Azo-PNIPAM. Moreover, by adjusting the duration of UV light exposure, arrested coalescence between liquid marbles is achieved, which provides possibilities for smart droplet-based microreactors and various liquid manipulations.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00543"},"PeriodicalIF":4.3,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145172259","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enrichment of Hyaluronic Acid Binding Tumor Cells by Modulation of Selective Adhesion on Microgel Surfaces.","authors":"Melanie Schmidt, Dilay Karayel, André Franken, Janita Müller, Laura Hartmann, Klaus Pantel, Tanja Fehm, Hans Neubauer, Stephan Schmidt","doi":"10.1002/marc.202500549","DOIUrl":"https://doi.org/10.1002/marc.202500549","url":null,"abstract":"<p><p>Liquid biopsy-based detection of cells with specific biomarker profiles is critical for cancer diagnostics and treatment. Here, we present a novel method for the selective enrichment of CD44-expressing tumor cells from blood using thermoresponsive microgel surfaces functionalized with hyaluronic acid (HA). A key feature of our approach is the precise modulation of CD44-HA interactions through the microgels' volume phase transition temperature (VPTT). Lowering the temperature from 37°C to 30°C induces swelling of the microgel layer, thereby diminishing adhesive interactions and promoting the detachment of weakly adhering white blood cells (WBCs), while strongly adherent tumor cells remain captured. Flow cytometry analysis studies further reveal that tumor cells with elevated CD44 expression exhibit persistent adhesion on HA-functionalized surfaces. Given the straightforward fabrication process and the versatility for incorporating various biomarkers via chemical synthesis, this temperature-responsive microgel platform holds promise for the efficient capture of circulating tumor cells (CTCs) present in the blood of cancer patients and other challenging diagnostic applications.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00549"},"PeriodicalIF":4.3,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129714","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}