{"title":"Molecular Dynamics Simulation of Cross-linked Epoxy Resins: Past and Future","authors":"Satoru Yamamoto, Keiji Tanaka","doi":"10.1002/marc.202570041","DOIUrl":"https://doi.org/10.1002/marc.202570041","url":null,"abstract":"<p><b>Front Cover</b>: Epoxy resins are cured by the reaction between epoxy and amine compounds to form a three-dimensional network. To better understand the curing process and crosslinking structure of epoxy resins, a treasure hunt using molecular dynamics simulations is conducted. More details can be found in article 2400978 by Satoru Yamamoto and Keiji Tanaka.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":"46 14","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/marc.202570041","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144647228","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Aggregation-Driven Fluorescence: Decoding Cooperative Artificial Motors Enable Bimodal Emission in Semi-Solid Biohybrid Systems.","authors":"Sudeshna Kalita, Anup Singhania, Amit Kumar Pathak, Prerna Chettri, Anirban Bandyopadhyay, Subrata Ghosh","doi":"10.1002/marc.202500334","DOIUrl":"https://doi.org/10.1002/marc.202500334","url":null,"abstract":"<p><p>Understanding the cooperative working principle of artificial rotary motors is essential for developing complex biohybrid systems. Such systems could enable critical tasks like proton and ion transport through artificial membranes or gating in artificial valves. To investigate cooperative transitions, we studied our double ratchet motor (DRM), composed of a Brownian rotor and a power stroke rotor, both coupled to a shared stator (-C≡C-). While DRMs exhibit stable rotary motion in compatible solvents, their integration into adaptive bio-synthetic systems remains challenging. We explored DRM behavior in a semi-solid chitosan matrix, revealing thermally activated metastable rotational states. The accumulation of these states led to aggregation-induced fluorescence emission, displaying both high-energy blue shifts and red shifts. We fabricated DRM-embedded chitosan hybrid films to investigate this bimodal emission, attributing DRM aggregation to binary solvent-induced clustering. These findings provide insight into the molecular mechanisms underpinning motor-driven fluorescence modulation. This study advances the potential of artificial motors in biohybrid materials, paving the way for their integration into biochemical reaction networks and adaptive synthetic systems.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00334"},"PeriodicalIF":4.2,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144648094","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}
Min Chen, Karen C Bustillo, Yen Jea Lee, Colin Ophus, Jim Ciston, Brooks A Abel, Xi Jiang, Nitash P Balsara, Andrew M Minor
{"title":"In Situ 4D-STEM Imaging of the Orientation of Lamellar Clusters in Polymer Crystallization.","authors":"Min Chen, Karen C Bustillo, Yen Jea Lee, Colin Ophus, Jim Ciston, Brooks A Abel, Xi Jiang, Nitash P Balsara, Andrew M Minor","doi":"10.1002/marc.202500450","DOIUrl":"https://doi.org/10.1002/marc.202500450","url":null,"abstract":"<p><p>In semi-crystalline polymeric materials, the initial stages of nucleation and the growth path of crystalline domains can determine the final performance. Here, we used four-dimensional scanning transmission electron microscopy (4D-STEM) imaging to analyze the changes in lamellar orientation in high-density polyethylene (HDPE) during heating and cooling. This method allowed us to quantitatively detect the formation of lamellae clusters with different in-plane orientations, which are not visible with traditional methods. Our analysis provided detailed insights into the orientation and size changes of crystalline domains. Additionally, this technique enabled direct observation of lattice structures in hierarchical lamellae and the growth of crystals, confirming the local variability in lamellar orientation. This innovative approach significantly improves our understanding of polymer crystallization, linking changes in morphology and lattice structures at different length scales.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00450"},"PeriodicalIF":4.2,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144648096","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}
Ewout Buijs, Zlata Nagorna, Joachim F R Van Guyse, Matthias Barz
{"title":"Synthesis of Heterotelechelic Poly(N-ethylglycine) Polymers: from Polypeptoid Lipid Conjugates to Protein-Polymer Conjugates.","authors":"Ewout Buijs, Zlata Nagorna, Joachim F R Van Guyse, Matthias Barz","doi":"10.1002/marc.202500422","DOIUrl":"https://doi.org/10.1002/marc.202500422","url":null,"abstract":"<p><p>The need for alternative hydrophilic polymers to polyethylene glycol (PEG) has intensified due to increasing concerns about immunogenicity and hypersensitivity reactions. In this work, we report the synthesis of well-defined heterotelechelic poly-N-ethylglycine (pNEtGly) via acid-catalyzed ring-opening polymerization of N-substituted N-carboxyanhydrides with a degree of polymerization from 25 to 400. The Leuchs synthesis was modified and optimized for the preparation of high-purity N-ethylglycine NCA monomers, enabling controlled polymerization with the use of organic acid catalysts. The resulting pNEtGly have low polydispersity values (Ð < 1.05) and quantitative end-group fidelity, enabling the synthesis of well-defined polymer-lipid and polymer-protein conjugates. A palmitamide-functionalized pNEtGly demonstrated near-quantitative conversion to polymer-lipid conjugates. Furthermore, maleimide-functionalized pNEtGly was conjugated to human serum albumin (HSA) via thiol-maleimide coupling, forming a protein-polymer conjugate with high purity. These results establish pNEtGly as another interesting hydrophilic polymer for biomedical applications, particularly in lipid-based drug delivery and bioconjugation strategies.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00422"},"PeriodicalIF":4.2,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144648100","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}
Jizeng Shang, Si Zhang, Xianping Qiu, Jian Zhang, Kaifeng Lin, Debin Xia, Lizhu Zhang, Yulin Yang
{"title":"Recent Advances in Modification and Application of Polyhedral Oligomeric Silsesquioxane/Polyurethane Composites: A Comprehensive Review.","authors":"Jizeng Shang, Si Zhang, Xianping Qiu, Jian Zhang, Kaifeng Lin, Debin Xia, Lizhu Zhang, Yulin Yang","doi":"10.1002/marc.202500337","DOIUrl":"https://doi.org/10.1002/marc.202500337","url":null,"abstract":"<p><p>Great challenges stand in the development of polyurethane (PU) due to its inherent flammability, suboptimal water resistance, and poor weather fastness. Polyhedral oligomeric silsesquioxane (POSS), acts as a classic nano-modifier with good biocompatibility, stability, non-toxicity, and easy-modification, also, widely used in various polymer fields. Introducing POSS into PU is a significant way to improve the defects and realize multifunctional modification. A brand-new comprehensive summary of POSS/PU materials over the past 5 years, including molecular characteristics, preparation methods, reaction mechanisms, intrinsic attributes, and practical applications, is presented in this manuscript. First, the structure and properties of PU and POSS are elucidated from the molecular perspective. Subsequently, the influence of POSS on the morphological structure, interfacial performance, mechanical attributes, and thermal properties of PU is systematically discussed, demonstrating the potential of POSS in improving novel PU materials. Finally, the research progress of POSS/PU composites in functional coatings, biomedical materials, flame-retardant materials, and solid energetic materials is emphatically introduced. Additionally, the review analyses a brief understanding of the challenges of POSS/PU composites in the research progress, and the following development directions are also prospected, providing an important reference for the production and applications of POSS/PU materials in the future.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00337"},"PeriodicalIF":4.2,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144648099","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}
Rumeng Gao, Yayu Feng, Yunfei Liu, Lin Wang, Kuilin Deng
{"title":"Preparation of PIE-Active Poly(2,4-thiazolidinediones) by Oxidative Polymerization and Simultaneous Specific Detection of Cu<sup>2+</sup>/Co<sup>2+</sup> Ions.","authors":"Rumeng Gao, Yayu Feng, Yunfei Liu, Lin Wang, Kuilin Deng","doi":"10.1002/marc.202500420","DOIUrl":"https://doi.org/10.1002/marc.202500420","url":null,"abstract":"<p><p>In this study, poly(2, 4-thiazolidinedione) (PTD) is prepared by oxidative polymerization using 2,4-thiazolidinedione (TD) as monomer. PTD exhibits significant polymerization-induced emission (PIE) at 540 nm, resulting from the intramolecular aggregation of thiazole heterocycles and the formation of electron-space conjugation. The PIE-active PTD demonstrates simultaneously specific detection of Cu<sup>2</sup>⁺/Co<sup>2</sup>⁺ with detection limits as low as 0.47 µM and 68.9 nM, respectively, even in the presence of 14 common metal ions and 11 anions. Fluorescence quenching experiments reveal that Cu<sup>2</sup>⁺/Co<sup>2</sup>⁺ coordinates with PTD to form a 1:2 non-fluorescent complex through a static quenching mode. Most importantly, the efficient differentiation between Cu<sup>2</sup>⁺ and Co<sup>2</sup>⁺ is achieved using dynamic color recognition technology based on smartphone APP and UV-vis absorption spectroscopy. This approach innovatively combines solution color gradient change with smartphone RGB to establish a semi-quantitative and convenient detection method. The lower detection limits of Cu<sup>2</sup>⁺/Co<sup>2</sup>⁺ reached 36.2 and 37.8 nMm with naked eye recognition, which provides a technological solution for the rapid detection of Cu<sup>2</sup>⁺/Co<sup>2</sup>⁺ ions without the aid of large-scale instruments. In brief, the successful preparation and detection application of PIE-active PTD open up a straightforward and feasible path for molecular design of fluorescent non-conjugated polymers from non-fluorescent monomers.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00420"},"PeriodicalIF":4.2,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144648098","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":"The Alchemist, the Scientist, and the Robot: Exploring the Potential of Human-AI Symbiosis in Self-Driving Polymer Laboratories.","authors":"Bahar Dadfar, Berna Alemdag, Gözde Kabay","doi":"10.1002/marc.202500380","DOIUrl":"https://doi.org/10.1002/marc.202500380","url":null,"abstract":"<p><p>Polymer chemistry research has progressed through three methodological eras: the alchemist's intuitive trial-and-error, the scientist's rule-based design, and the robot's algorithm-guided automation. While approaches combining combinatorial chemistry with statistical design of experiments offer a systematic approach to polymer discovery, they struggle with complex design spaces, avoid human biases, and scale up. In response, the discipline has adopted automation and artificial intelligence (AI), culminating in self-driving laboratories (SDLs), integrating high-throughput experimentation into closed-loop, AI-assisted design-build-test-learn cycles, enabling the rapid exploration of chemical spaces. However, while SDLs address throughput and complexity challenges, they introduce new forms of the original problems: algorithmic biases replace human biases, data sparsity creates constraints on design space navigation, and black-box AI models create transparency issues, complicating interpretation. These challenges emphasize a critical point: complete algorithmic autonomy is inadequate without human involvement. Human intuition, ethical judgment, and domain expertise are crucial for establishing research objectives, identifying anomalies, and ensuring adherence to ethical constraints. This perspective supports a hybrid model grounded in symbiotic autonomy, where adaptive collaboration between humans and AI enhances trust, creativity, and reproducibility. By incorporating human reasoning into adaptive AI-assisted SDL workflows, next-generation autonomous polymer discovery will be not only faster but also wiser.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00380"},"PeriodicalIF":4.2,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144648075","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}
Federica Zaccagnini, Francesca Petronella, Michael E McConney, Jonathan Slagle, Kwang-Un Jeong, Timothy J Bunning, Luciano De Sio
{"title":"Thermoplasmonic-Controlled Optical Filters Based on the Combination of Chiral Liquid Crystals and Metasurfaces.","authors":"Federica Zaccagnini, Francesca Petronella, Michael E McConney, Jonathan Slagle, Kwang-Un Jeong, Timothy J Bunning, Luciano De Sio","doi":"10.1002/marc.202500339","DOIUrl":"https://doi.org/10.1002/marc.202500339","url":null,"abstract":"<p><p>A novel class of photonic filters is obtained by integrating a large-area optical plasmonic metasurface with a broadband cholesteric liquid crystal (CLC) Bragg reflector. By utilizing the photo-thermal characteristics of the optical plasmonic metasurface, the reflection properties of the CLC layer can be manipulated. The thermally induced variation of the CLC's pitch and the refractive index produces a reversible blue-redshift of the reflection band of about 80 nm. The synergistic interaction between these two effects enables the development of innovative optical color filters that integrate a light-tunable mirror and a controllable optical absorber.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00339"},"PeriodicalIF":4.2,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144648076","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":"Effect of Photoinitiation Process on Photo-Crosslinking of Gelatin Methacryloyl Hydrogel Networks.","authors":"Doğukan Duymaz, İsmail Can Karaoğlu, Seda Kizilel","doi":"10.1002/marc.202500376","DOIUrl":"https://doi.org/10.1002/marc.202500376","url":null,"abstract":"<p><p>Gelatin methacryloyl (GelMA) has emerged as a widely utilized biomaterial in tissue engineering due to its tunable mechanical properties, cell-adhesive motifs, and photo-crosslinkability. However, the physicochemical characteristics and biomedical utility of GelMA hydrogels are greatly influenced by the choice and concentration of photoinitiating systems. Despite increasing acceptance of visible-light and UV-sensitive initiators, a systematic comparative evaluation of their impact on GelMA hydrogel properties has not been studied. In this study, we present the first systematic investigation of how individual photoinitiators, Eosin Y (EY), Lithium Phenyl-2,4,6-trimethylbenzoylphosphinate (LAP), Ruthenium (II) trisbipyridyl chloride ([RuII(bpy)<sub>3</sub>]<sup>2+</sup>) (Ru), affect the viscoelastic properties, swelling behavior, degradation kinetics, and cytocompatibility of 5% and 10% (w/v) GelMA hydrogels. Through alteration of photoinitiator concentrations ([EY]: 0.005-0.1 mM, [LAP]: 0.01-0.5% (w/v), [Ru]: 0.02-1 mM) and utilizing consistent light intensity (10 mW/cm<sup>2</sup> at system-specific wavelengths), we identified critical thresholds and plateau behaviors that distinctly influenced the stiffness and integrity of the hydrogels. Our findings revealed that each photoinitiating system exhibits unique advantages and trade-offs. LAP and Ru systems facilitated rapid gelation with easier utilization and were associated with higher swelling and accelerated degradation profiles-features particularly advantageous for applications such as 3D bioprinting and in situ injectable hydrogel systems. However, their atypical behaviors at certain concentrations and light exposure durations highlight the necessity for precise control and further mechanistic exploration. In contrast, EY-mediated hydrogels offered superior stiffness and minimal swelling at optimal concentrations, favoring applications that demand long-term mechanical stability, at the cost of a more complex cross-linking mechanism. Notably, by correlating mechanical and degradation behaviors with NIH-3T3 fibroblast viability, we also assessed biocompatibility window for each concentration of the systems, linking biomaterial performance with biomedical applicability. Overall, our study underlines the importance of tailoring photoinitiator selection and concentration for specific application needs, striking a balance between gelation kinetics, mechanical integrity, degradation behavior, and cytocompatibility. These insights provide a foundational framework for engineering GelMA-based hydrogels, paving the way for reproducible, efficient, targeted biomedical applications.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00376"},"PeriodicalIF":4.2,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144648095","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}